Article
Chemistry, Analytical
Kanako Inoue, Akimasa Fujihara
Summary: Free D-amino acids and amino acid isomers were differentiated using tandem mass spectrometry without chromatographic separation. UV photodissociation and water adsorption of Leu and Ile enantiomers hydrogen-bonded with Trp were investigated. The results showed that enantiomer-selective bond cleavage of Trp was observed, and the stronger intermolecular interactions within the homochiral cluster hindered enantiomer-selective photodissociation.
JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS
(2023)
Article
Biochemical Research Methods
Amanda R. Bubas, Evan Perez, Luke J. Metzler, Scott D. Rissler, Michael J. Van Stipdonk
Summary: This study investigates the collision-induced dissociation of [UO2(NO3)(3)](-) and [UO2(NO3)(2)(O-2)](-), as well as the CID of [UO2(NO3)(O-2)](-) and the resulting product ions. DFT calculations identified pathways for the generation of product ions, revealing that the composition of [UO2(O)(NO2)](-) is [UO2(O)(NO2)](-) rather than [UO2(NO3)](-).
JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Biochemical Research Methods
Hiromori Murashima, Akimasa Fujihara
Summary: The study investigated chiral recognition between amino acids and monosaccharides in the gas phase as a model for chemical evolution in interstellar molecular clouds. Results showed that the optical properties of Trp in the clusters induced by 285-nm photoexcitation were useful for identifying and quantifying pentose enantiomers. Additionally, pentose enantiomeric excess in solution could be determined from relative abundances observed in a single product ion spectrum of 285-nm photoexcited hydrogen-bonded clusters of H+(L-Trp) and pentose.
ANALYTICAL BIOCHEMISTRY
(2021)
Article
Biochemical Research Methods
Elvin R. Cabrera, Brian H. Clowers
Summary: This study describes a method of modulating the ion gates of ion mobility spectrometry using a discrete stepwise function, achieving synchronization between the generated frequencies and the scan rate of the linear ion trap. This method eliminates the ambiguity of assigning the ion current derived from a single modulation frequency and maintains high levels of precision across different combinations.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Biochemical Research Methods
Hsi-Chun Chao, Kenneth W. Lee, Mack Shih, Scott A. McLuckey
Summary: Electrospray ionization (ESI) of large polymeric molecules has the characteristic of generating charge state distributions. When a distribution of polymers is subjected to ESI, the charge state distribution of each component can lead to a mass spectrum composed of a highly congested mixture of ions with overlapping mass-to-charge (m/z) ratios. The overlap of charge state distributions of homopolymers can give rise to an Emerald City pattern in the mass spectrum, which consists of a dense central cluster of peaks with similar m/z values and wing-like patterns on either side. Parameters were studied for their contributions to the appearance of Emerald City patterns. Experimental validation was done using dextran samples and a web-based tool was developed. A strategy involving direct infusion ESI-MS coupled with segmented m/z windows and gas-phase proton transfer reactions was proposed for characterizing polydisperse synthetic polymer samples, with poly(ethylenimine) samples used as model systems.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Chemistry, Physical
Daiya Nagai, Akimasa Fujihara
Summary: The effects of intermolecular interactions on the reactivity of hydrogen-bonded clusters of adenosine and tryptophan in the gas phase were investigated using water adsorption and ultraviolet photoexcitation. The results showed that water adsorption weakened the intermolecular interactions between adenosine and tryptophan in the clusters and inhibited the photoinduced glycosidic bond cleavage of adenosine.
Article
Biochemical Research Methods
Elvin R. Cabrera, Brian H. Clowers
Summary: By casting ion population's mobility information in the frequency domain, time-dispersive ion mobility techniques can now be compatible with slower mass analyzers like ion traps. Recent progress has been made in maximizing the efficiency of Fourier transform ion mobility-mass spectrometry (FT-IM-MS) experiments, but the intersection between practical implementation considerations and theoretical limits of traditional signal processing techniques needs to be further explored. The importance of avoiding signal aliasing due to undersampling signals, along with evaluating limitations imposed by experimental parameters, is crucial for successful Fourier-based multiplexing experiments.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Engineering, Multidisciplinary
Xiang Fang, Jie Xie, Shiying Chu, You Jiang, Yuting An, Chang Li, Xiaoyun Gong, Rui Zhai, Zejian Huang, Chunling Qiu, Xinhua Dai
Summary: In this study, a quadrupole-linear ion trap (Q-LIT) tandem mass spectrometer was designed and built for the accurate and efficient measurement of small molecule disease markers. The developed method demonstrated high sensitivity and resolution, simplified the pre-treatment process, and showed potential for biomarker determination in clinical diagnosis and therapeutics.
Article
Chemistry, Analytical
Erlu Feng, Xin Ma, Hilkka Kenttamaa
Summary: Substituted ureas are a class of organic compounds commonly used in agriculture and chemical fields, and distinguishing them from other compounds with similar structures can be challenging. A four-stage tandem mass spectrometry method (MS4) was introduced in this study to differentiate between different ureas and similar compounds. The method utilizes gas-phase ion-molecule reactions followed by collision-activated dissociation (CAD) steps to generate diagnostic fragment ions that can effectively distinguish ureas, amides, and carbamates.
ANALYTICAL CHEMISTRY
(2021)
Article
Biochemical Research Methods
Sarah Schleicher, Inka-Rosalia Lottje, Petra Mischnick
Summary: Accurate quantification of isotopologous mixed O-methyl-O-methyl-d(3)-cellooligosaccharides was achieved through investigation into ionization processes with an electrospray ionization ion trap mass spectrometer. By optimizing experimental conditions, potential bias during MS measurement was effectively addressed.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2022)
Article
Biochemical Research Methods
Sarah Schleicher, Dominik Horoba, Philip Krafzig, Petra Mischnick
Summary: In this study, the hydroxyethyl substitution in cellulose ethers was analyzed using ESI-IT-MS. The correct quantification of the constituents was achieved through the use of internal standards and optimization of measurement conditions. The study also highlighted potential errors in relative quantification when using internal standards with similar chemistry or for analytes with related structures.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Chang Li, Shiying Chu, Siyuan Tan, Xinchi Yin, You Jiang, Xinhua Dai, Xiaoyun Gong, Xiang Fang, Di Tian
Summary: This review discusses the latest developments in mass analyzers to improve the sensitivity of mass spectrometers. The advantages and limitations of different mass analyzers and their combinations are compared and discussed. It provides guidance for the selection of suitable mass spectrometers in chemical and biological analytical applications.
FRONTIERS IN CHEMISTRY
(2021)
Article
Computer Science, Information Systems
Shobha Sharma, Tarun Varma
Summary: This paper extends the discrete combined Fourier transform (DCFT) to the fractional Fourier transform (FrFT) domains and explores its applications in image enhancement. The proposed discrete combined fractional Fourier transform (DCFrFT) is a generalized version of DCFT. Simulation results demonstrate the effectiveness of the proposed DCFrFT and its application in image recovery. The enhancement approach in the proposed transform domain improves degraded images with the appropriate parameter selection.
MULTIMEDIA TOOLS AND APPLICATIONS
(2023)
Article
Physics, Multidisciplinary
A. Igarashi, D. Kato
Summary: In this study, collisions between proton and helium were studied using a semi-classical atomic orbital expansion method, with the explicit consideration of two electrons. Differential cross sections with respect to the projectile scattering angle were calculated for various processes including elastic scattering, 2(1)S and 2(1)P excitation, single electron capture, and single ionization. The results show good agreement with experiments, except for a few discrepancies in elastic scattering and single electron capture with target excitation.
Article
Chemistry, Multidisciplinary
Sophie R. Harvey, Zachary L. VanAernum, Vicki H. Wysocki
Summary: Negative mode ionization of protein complexes offers closer-to-native structural information with avoided peak broadening caused by solution phase charge reduction additives. It also provides direct structural information when coupled with SID.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Analytical
Anthony M. Pitts-McCoy, Abdirahman M. Abdillahi, Kenneth W. Lee, Scott A. McLuckey
Summary: Native mass spectrometry (MS) using negative-ion polarity facilitates charge state determination in heterogeneous mixtures by attaching multiply charged ions. This approach provides broad mass-to-charge ratio information and overcomes challenges associated with narrow charge state distributions. The utility of multiply charged cation attachment is demonstrated in the analysis of complex ions and mixtures, enabling precise charge state assignments and revealing missing components.
ANALYTICAL CHEMISTRY
(2022)
Article
Biochemical Research Methods
Joshua L. Fischer, Samantha A. Mehnert, Anthony M. Pitts-McCoy, Scott A. McLuckey
Summary: In this study, nucleophilic substitution covalent modification ion/ion reactions between peptides and sulfobenzoic acid esters were carried out in a linear quadrupole ion trap. The results showed that the kinetics of the reaction were highly sensitive to the nucleophilic sites on the peptides, the leaving groups on the reagent, and the location of the attachment sites on the reagent and analyte. Significant variations in activation energy or entropy were found to underlie the measured rate differences depending on the identity of the analyte/reagent combination.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Chemistry, Physical
John T. Lawler, Christopher P. Harrilal, Andrew F. DeBlase, Edwin L. Sibert, Scott A. McLuckey, Timothy S. Zwier
Summary: This study investigated the role of d-Proline in forming beta-hairpin loops in short protonated peptides and found that it plays a crucial role in forming type II beta-turns. The unstructured peptides were influenced by the protonated peptides, and the structure of peptides forming beta-hairpin loops was affected by steric and charge-induced effects.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Biochemical Research Methods
Hsi-Chun Chao, Kenneth W. Lee, Mack Shih, Scott A. McLuckey
Summary: Electrospray ionization (ESI) of large polymeric molecules has the characteristic of generating charge state distributions. When a distribution of polymers is subjected to ESI, the charge state distribution of each component can lead to a mass spectrum composed of a highly congested mixture of ions with overlapping mass-to-charge (m/z) ratios. The overlap of charge state distributions of homopolymers can give rise to an Emerald City pattern in the mass spectrum, which consists of a dense central cluster of peaks with similar m/z values and wing-like patterns on either side. Parameters were studied for their contributions to the appearance of Emerald City patterns. Experimental validation was done using dextran samples and a web-based tool was developed. A strategy involving direct infusion ESI-MS coupled with segmented m/z windows and gas-phase proton transfer reactions was proposed for characterizing polydisperse synthetic polymer samples, with poly(ethylenimine) samples used as model systems.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Biochemical Research Methods
Kenneth W. Lee, Austin Z. Salome, Michael S. Westphall, Timothy Grant, Joshua J. Coon
Summary: Addressing mixtures and heterogeneity in structural biology requires approaches that can differentiate and separate structures based on mass and conformation. Mass spectrometry (MS) provides tools for measuring and isolating gas-phase ions. The matrix-landing approach uses native MS to probe and select biomolecular ions for subsequent TEM imaging, thus unifying information available via native MS with TEM images. The results show that these complexes maintain their structure through gas-phase isolation.
JOURNAL OF PROTEOME RESEARCH
(2023)
Review
Chemistry, Analytical
Hsi-Chun Chao, Scott A. McLuckey
Summary: Gas-phase ion/ion reactions can efficiently alter the ion types of analytes for improved structural characterization. This is particularly useful for lipid analysis, where diverse chemical species and isomers exist. Gas-phase ion/ion reactions have been shown to enhance the ability of tandem mass spectrometry in lipid structural characterization. This review provides an overview of the progress in the application of gas-phase ion/ion reactions in lipid analysis.
TRAC-TRENDS IN ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Analytical
Kimberly C. Fabijanczuk, James W. Hager, Scott A. McLuckey
Summary: Conventional electrospray ionization (ESI) of mixtures can complicate the analysis of individual components due to the overlap of singly and multiply charged analyte species. To address this challenge, a gas-phase approach was employed to separate singly charged ions from a population of ions of mixed charge states. The method allows for improved signal-to-noise ratio and retention of spatially separated ions within a mass spectrometer.
ANALYTICAL CHEMISTRY
(2023)
Article
Biochemical Research Methods
De'Shovon M. Shenault, Scott A. McLuckey, Elissia T. Franklin
Summary: Shotgun lipid analysis using ESI-MS/MS is a common method for identifying and characterizing GPs. However, determining certain structural features such as carbon-carbon double bonds and cyclopropane rings can be challenging. This study demonstrates the use of gas-phase charge inversion reactions in combination with CID to provide more detailed structural elucidation of GPs.
JOURNAL OF MASS SPECTROMETRY
(2023)
Article
Biochemical Research Methods
Yue Fu, Christopher J. Brown, Joshua T. Johnson, Brett M. Marsh, Jeffrey R. Gilbert, Erlu Feng, Hilkka I. Kenttamaa
Summary: Tandem mass spectrometry using diagnostic gas-phase ion-molecule reactions is a reliable method for identifying functional groups in unknown compounds. This study modified a high-resolution mass spectrometer with a portable reagent inlet system to obtain high-resolution data for ion-molecule reactions. The modified instrument was able to differentiate between isobaric ions and examine the structures of fragment ions generated during collision-induced dissociation.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Chemistry, Analytical
Kimberly C. Fabijanczuk, David J. Foreman, Scott A. McLuckey
Summary: Electrospray ionization (ESI) of mixtures can produce ions with different masses and charges, resulting in overlapping mass to-charge (m/z) ratios. To address this issue, researchers have developed a gas-phase method using ion/ion reactions to invert the charge of anionic lipid species using ytterbium(III) and a specific ligand, allowing for chemical separation of doubly and singly charged anions.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Analytical
Nicole M. Brundridge, Jonathan Dickerhoff, Danzhou Yang, Scott A. Mcluckey
Summary: This study investigates the preservation and stability of G-quadruplex (G4) DNA structure in gas phase using mass spectrometry. The results show that G4 structure exhibits distinct fragmentation behavior compared to non-G4 structure under low energy activation, indicating its stability in the gas phase.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Analytical
Michael S. Westphall, Kenneth W. Lee, Colin Hemme, Austin Z. Salome, Keaton Mertz, Timothy Grant, Joshua J. Coon
Summary: This article describes an apparatus that can cryogenically land particles from the ion beam of a mass spectrometer onto transmission electron microscope grids for cryo-electron microscopy. This system also allows for the controlled formation of thin films of amorphous ice on the grid surface. The study demonstrates that using this cryogenic landing device significantly improves the structural preservation of deposited protein-protein complexes compared to room temperature landings, and landing under cryogenic conditions can increase the diversity of particle orientations, enabling improved 3D structural interpretation.
ANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Analytical
Kimberly C. Fabijanczuk, Hsi-Chun Chao, Joshua L. Fischer, Scott A. McLuckey
Summary: Phosphoinositides, phosphorylated derivatives of phosphatidylinositols, are crucial signaling phospholipids in mammalian cellular membranes. Identifying and characterizing these phosphoinositides and their isomers accurately using traditional shotgun mass spectrometry is challenging. However, utilizing novel gas-phase ion/ion chemistry expands the range of precursor ion-types and allows for structural characterization of phosphoinositides. This method provides valuable information on the phosphorylation degree, fatty acyl composition, and isomeric species.
Article
Chemistry, Inorganic & Nuclear
Kimberly C. Fabijanczuk, Weam A. O. Altalhi, Asma M. O. Aldajani, Allan J. Canty, Scott A. McLuckey, Richard A. J. O'Hair
Summary: In this study, gas-phase reactions between tris-1,10-phenantholine metal dications and tetraphenylborate anions were investigated. The formation of ion-pairs and subsequent organometallic complex formation were observed. DFT calculations confirmed the energy barriers and hydrolysis reactions in accordance with experimental results.
DALTON TRANSACTIONS
(2022)