Article
Chemistry, Multidisciplinary
Fangshun Yang, Raphael D. Urban, Jonas Lorenz, Jan Griebel, Nima Koohbor, Markus Rohdenburg, Harald Knorke, Daniel Fuhrmann, Ales Charvat, Bernd Abel, Vladimir A. Azov, Jonas Warneke
Summary: Despite its primarily analytical function, mass spectrometry also has potential as a synthetic tool, facilitating advanced synthesis routes by reactions in charged microdroplets or ionic thin layers. In this study, two preparative mass spectrometry methods were used to generate products at a nanomolar scale, allowing for further characterization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kai-Hung Huang, Zhenwei Wei, R. Graham Cooks
Summary: Microdroplets exhibit unique interfacial chemistry, accelerating reactions compared to bulk systems. This study found that carbon dioxide reacts with amines at the droplet interface to form carbamic acids. Additionally, the presence of trace amounts of water can enhance the reaction by potentially forming superacid or superbase at the water interface.
Article
Chemistry, Multidisciplinary
Habib Gholipour-Ranjbar, Hugo Y. Samayoa-Oviedo, Julia Laskin
Summary: In this study, activated nanoclusters were prepared through controlled ligand removal in the gas phase using an ion soft-landing instrument. It was found that nanoclusters with one ligand removed showed selective dimerization on self-assembled monolayer surfaces, while nanoclusters with two ligands removed underwent nonselective reactions and formed larger fused clusters. This study reveals the potential of using fragment ions for activating and depositing nanoclusters.
Article
Chemistry, Analytical
Hugo Y. Samayoa-Oviedo, Kay-Antonio Behrend, Sebastian Kawa, Harald Knorke, Pei Su, Mikhail E. Belov, Gordon Anderson, Jonas Warneke, Julia Laskin
Summary: The development of a new instrument allows for high-flux electrospray ionization-based soft landing of mass-selected fragment ions onto surfaces, enabling high-coverage deposition and investigation of gaseous fragment ions reactivity in the condensed phase. The observed reactions of deposited fragment ions depend on the ion structure and the composition of co-deposited species on the surface.
ANALYTICAL CHEMISTRY
(2021)
Review
Chemistry, Physical
Venkateshkumar Prabhakaran, Grant E. Johnson, Julia Laskin
Summary: Ion soft landing is a mass spectrometry technique that allows the controlled deposition of selected ions onto surfaces. It is useful for studying the electrochemical properties of well-defined ions and characterizing redox-active species. Ion soft landing has the advantage of enabling the study of complex molecules and clusters that cannot be purified using traditional methods. It also allows for the precise preparation and characterization of electrode-electrolyte interfaces for various applications.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Margot De Spiegeleer, Vera Plekhova, Jozefien Geltmeyer, Ella Schoolaert, Beata Pomian, Varoon Singh, Kathleen Wijnant, Kimberly De Windt, Volter Paukku, Alexander De Loof, Inge Gies, Nathalie Michels, Stefaan De Henauw, Marilyn De Graeve, Karen De Clerck, Lynn Vanhaecke
Summary: In recent years, ambient ionization mass spectrometry (AIMS) has allowed for direct analysis of biofluid metabolome. However, AIMS procedures are hindered by analytical and practical limitations, which affect metabolome coverage. This study aimed to develop biofluid-specific metabolome sampling membranes (MetaSAMPs) to improve AIMS. Customized MetaSAMPs made of hydrophilic and lipophilic polymers demonstrated superior metabolome coverage and transport stability compared to crude biofluid analysis. This new approach was successfully validated and has potential applications in metabolic health stratification.
Review
Chemistry, Analytical
Weixiang Li, Jianghui Sun, Yixuan Gao, Ying Zhang, Jin Ouyang, Na Na
Summary: The monitoring of EC reactions by ambient mass spectrometry (AMS) provides structural information of analytes, potential for detecting short-lived intermediates, examining reaction mechanisms, and discovering new reactions, contributing significantly to fields including biological chemistry, electrocatalysis, organic synthesis or battery fabrication. Various designs of EC-coupled electrospray ionization-based AMS systems, addressing advantages, limitations, and proposed suggestions for future developments, are summarized in this review.
TRAC-TRENDS IN ANALYTICAL CHEMISTRY
(2021)
Article
Physics, Atomic, Molecular & Chemical
Chiara Salvitti, Anna Troiani, Franco Mazzei, Cristine D'Agostino, Rosaceleste Zumpano, Chiara Baldacchini, Anna Rita Bizzarri, Alessandra Tata, Federico Pepi
Summary: This study demonstrates that an unmodified ESI Z-spray source can successfully carry out ambient ion soft landing, showing its potential in studying accelerated microdroplet reactions.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Chemistry, Physical
Jan Postulka, Petr Slavicek, Andriy Pysanenko, Viktoriya Poterya, Michal Farnik
Summary: Nanoparticles can provide efficient reaction environments for bimolecular reactions by controlling the formation rate of reaction pairs. In this study, we investigated electron-induced reactions in hydrogen peroxide in two types of nanoparticle environments and found that the reaction rate was faster in argon nanoparticles than in water nanoparticles. Computational simulations and mass spectrometry experiments were used to identify the reaction products and confirm the findings.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Analytical
Yuze Li, Junyu Chen, Lingwei Meng, Liuying He, Huihui Liu, Caiqiao Xiong, Zongxiu Nie
Summary: The MasSpec Pointer is a wireless pocket-size device powered by a 3.7 V polymer Li battery, which can be used for ambient ionization mass spectrometry. It has stable discharge and good quantification performance, allowing for quick testing of various samples in both positive and negative ion modes. The device can detect pesticides, chemicals, and other substances without any modification, and has a detection limit lower than 0.1 ng/mL for atrazine.
ANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Analytical
Maryam Aghaei, Annemie Bogaerts
Summary: In this study, plasma chemistry in a helium flowing atmospheric pressure afterglow (FAPA) for analytical spectrometry is described using a quasi-one-dimensional plasma chemical kinetics model. The model demonstrates the formation of H, N, and O atoms in the discharge region, and the dominance of O-3 and NO species in the afterglow. Helium plays a key role in Penning ionization and charge transfer reactions, leading to high analytical sensitivity. The model's predictions align with previous observations in the literature, providing insights to enhance analytical performance of ambient desorption/ionization sources.
ANALYTICAL CHEMISTRY
(2021)
Article
Optics
S. Gerlach, F. Balling, A. K. Schmidt, F. E. Brack, F. Kroll, J. Metzkes-Ng, M. Reimold, U. Schramm, M. Speicher, K. Zeil, K. Parodi, J. Schreiber
Summary: Recent advancements in laser-accelerated proton bunches have allowed for the reconstruction of energy distribution and monitoring of changes in energy spread and lateral size of individual bunches. Using I-BEAT 3D with ultrasonic transducers and fast data analysis, real-time measurements of mean energy, lateral position, and particle number are now possible with sub-MeV and sub-mm resolution.
HIGH POWER LASER SCIENCE AND ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Matthew J. Mcdermott, Brennan C. Mcbride, Corlyn E. Regier, Gia Thinh Tran, Yu Chen, Adam A. Corrao, Max C. Gallant, Gabrielle E. Kamm, Christopher J. Bartel, Karena W. Chapman, Peter G. Khalifah, Gerbrand Ceder, James R. Neilson, Kristin A. Persson
Summary: Synthesis is a major challenge in the discovery of new inorganic materials. The researchers introduced two selectivity metrics to assess the favorability of target/impurity phase formation in solid-state reactions, and used these metrics to analyze and rank existing approaches in the literature. They also developed a data-driven synthesis planning workflow and demonstrated its application in the synthesis of barium titanate.
ACS CENTRAL SCIENCE
(2023)
Article
Materials Science, Ceramics
G. Gutierrez, M. Bricout, F. Garrido, A. Debelle, L. Roux, C. Onofri
Summary: It was found that electronic energy dissipation has a significant acceleration effect on the formation and evolution of defects induced by nuclear energy deposition, and the magnitude of this acceleration depends on both the electronic energy loss level and the microstructure at the moment when the coupling occurs.
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Yuan Li, Yuanji Gao, Binpeng Zhan, Weiwei Chen, Fengjian Chu, Hongru Feng, Zhan Gao, Zihan Ma, Yuanjiang Pan
Summary: The salinity tolerance of ambient electric arc ionization (AEAI) was evaluated and compared with electrospray ionization (ESI) for different salt concentrations. AEAI-mass spectrometry (AEAI-MS) showed better signal intensity and quantitative ability in high salt concentrations. AEAI-MS successfully analyzed samples at high concentrations and even in saturated salt solutions.
CHINESE CHEMICAL LETTERS
(2022)
Article
Biochemical Research Methods
Shuli Tang, Licheng Fan, Heyong Cheng, Xin Yan
Summary: A new method utilizing AC-induced electroepoxidation reaction and nanoelectrospray ionization was developed to locate carbon-carbon double-bonds in lipids with positive and negative charges simultaneously. The AC voltage played multiple roles in initiating electro-epoxidation and protonation/deprotonation of lipids. This method was effective in lipid standards mixtures and a biological polar lipid extract, showing potential for wide applications in lipid-related research.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2021)
Review
Chemistry, Multidisciplinary
Dallas Freitas, Xi Chen, Heyong Cheng, Austin Davis, Blake Fallon, Xin Yan
Summary: The hyphenation of electrochemistry and mass spectrometry has become a powerful tool for studying redox processes. Various approaches are available, including integrating chromatography/electrophoresis, coupling EC flow cell to a mass spectrometer, and performing electrochemical reactions inside the ion source of a mass spectrometer. The development of modified ion sources allowing compatibility of electrochemistry with ionization processes allows for diverse applications in different studies.
Article
Physics, Atomic, Molecular & Chemical
Xin Yan
Summary: Recent studies have shown that microdroplets at the air/solution interface can achieve remarkable reaction acceleration. The unique environment of microdroplets can facilitate thermodynamically unfavorable reactions, impacting various fields including chemical derivatization and high-throughput reaction screening. Research has revealed the unique reactivities in microdroplets, acceleration mechanisms, and methods for scaling up reactions in this environment.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Chemistry, Multidisciplinary
Heyong Cheng, Tingyuan Yang, Madison Edwards, Shuli Tang, Shiqing Xu, Xin Yan
Summary: Development of new transition-metal-catalyzed electrochemistry is important for improving synthetic efficiency. In this study, an integrated platform for online screening of electrochemical transition-metal catalysis is described. This platform utilizes nano-ESI-MS and picomole-scale anodic corrosion to generate and evaluate cationic catalysts for mild electrocatalysis. The power of this platform is demonstrated by identifying electrolytic Pd-catalyzed Suzuki coupling, discovering Pd-catalyzed electrochemical C-H arylation, developing cascade reactions, and achieving late-stage functionalization of drug molecules. The scale-up reactions confirm the feasibility of the new electrochemical pathways discovered. Mechanistic studies using MS reveal the critical role of anodically generated cationic Pd catalyst. The novel online electrochemical screening platform and efficient cationic Pd catalyst hold great potential for discovering mild transition-metal-catalyzed reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tingyuan Yang, Shuli Tang, Syuan-Ting Kuo, Dallas Freitas, Madison Edwards, Hongying Wang, Yuxiang Sun, Xin Yan
Summary: Accurate measurement of lipid concentrations is crucial for understanding their functions and identifying disease biomarkers. A novel isobaric tag labelling strategy has been developed to address the challenges in lipid quantification, allowing determination of lipid isomers, relative quantification of unsaturated lipids, and improved ionization efficiencies of nonpolar lipids. This method has been successfully applied to characterize and quantify various types of lipids, including CE lipids in Alzheimer's disease serum.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Analytical
Shuli Tang, Xin Yan, Yuepeng Ke, Xi Chen, Fen Wang
Summary: In this study, we cascaded two electrochemical reactions in nanoelectrospray and achieved switching at different voltages. This allowed us to identify lipid structural isomers at multiple levels using mass spectrometry, and we demonstrated its application in analyzing healthy and cancerous samples.
ANALYTICAL CHEMISTRY
(2022)
Article
Physics, Atomic, Molecular & Chemical
Syuan-Ting Kuo, Shuli Tang, David H. Russell, Xin Yan
Summary: This study reports a method for characterizing the positional and geometric isomers of phospholipids using copper (I) ion complexed with phospholipids. By applying multi-stage fragmentation and measuring collision cross sections, the method enables rapid and effective distinction of isomers in lipid samples.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Biochemistry & Molecular Biology
Kai S. Yang, Lauren R. Blankenship, Syuan-Ting Alex Kuo, Yan J. Sheng, Pingwei Li, Carol A. Fierke, David H. Russell, Xin Yan, Shiqing Xu, Wenshe Ray Liu
Summary: As a novel covalent modification, a Y-shaped, S-O-N-O-S-bridged post-translational cross-link connecting three residues C22, C44, and K61 in the main protease (M-Pro) of SARS-CoV-2 was frequently observed during crystallographic analyses. This cross-link potentially serves as a redox switch to regulate the catalytic activity of M-Pro, a drug target of COVID-19. Targeting the open active site formed by this linkage could be a potential strategy for the development of SARS-CoV-2 antivirals, especially in combination with other active-site-targeting molecules such as paxlovid.
ACS CHEMICAL BIOLOGY
(2023)
Article
Biochemical Research Methods
Dallas P. Freitas, Xi Chen, Erin A. Hirtzel, Madison E. Edwards, Joohan Kim, Hongying Wang, Yuxiang Sun, Klaudia I. Kocurek, David Russell, Xin Yan
Summary: In this study, we developed an in situ droplet-based derivatization method for rapid analysis of tissue lipids at multiple isomer levels. The method involves on-tissue derivatization using the TriVersa NanoMate LESA pipette, followed by extraction and analysis of the derivatized lipids using chip-based LESA mass spectrometry (MS) and tandem MS. This approach enables characterization of lipid isomers at the carbon-carbon double-bond positional and sn-positional levels, as well as relative quantitation based on diagnostic ion intensities. The method allows for multiple derivatizations at different spots in the same functional region of an organ, facilitating orthogonal lipid isomer analysis using a single tissue slide. Lipid isomers in different regions of the mouse brain were profiled, demonstrating the potential of this droplet-based derivatization method in tissue lipid studies requiring fast sample-to-result turnovers.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tian Qiao, Madison E. E. Edwards, Xueting Tang, Xin Yan, Dong Hee Son
Summary: Despite the challenges posed by reverse charge transfer or charge recombination, cesium lead halide (CsPbX3) nanocrystals can selectively generate stable aminium or aminyl radicals from amines by controlling the imbalance of electron and hole populations achieved through varying the solvent composition. In the presence of dihalomethane, the irreversible removal of electrons enables efficient oxidative generation of aminium radicals. In the absence of dihalomethane, the availability of both electrons and holes leads to the production of aminyl radicals via sequential hole transfer and reductive N-H bond dissociation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemical Research Methods
Erin Hirtzel, Madison Edwards, Dallas Freitas, Ziying Liu, Fen Wang, Xin Yan
Summary: In this study, the N-H aziridination method was introduced to target carbon-carbon double bonds in nonpolar sterol lipids. The method significantly improved the lipid ionization efficiency and allowed for the identification and characterization of sterol isomers. Aziridination-assisted mass spectrometric analysis showed high efficiency, specificity, and quantitative analysis ability, making it suitable for broad applications in nonpolar lipid research.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Chemistry, Analytical
Madison E. Edwards, Dallas P. Freitas, Erin A. Hirtzel, Nicholas White, Hongying Wang, Laurie A. Davidson, Robert S. Chapkin, Yuxiang Sun, Xin Yan
Summary: Lipids are important biomarkers for disease diagnostics, and their analysis is limited by structural diversity and small sample volumes. In this study, a strategy was developed to extract lipids from small-volume samples and characterize their isomeric structures using mass spectrometry. The platform was successfully applied to analyze lipids from small-volume human plasma and Alzheimer's disease mouse serum samples. The method holds great potential for disease diagnosis and prevention.
ANALYTICAL CHEMISTRY
(2023)
Article
Physics, Atomic, Molecular & Chemical
Annesha Sengupta, Madison E. Edwards, Xin Yan
Summary: This study demonstrates the use of dual metal anodic corrosion as a method to simultaneously characterize and identify lipids at multiple isomer levels.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2023)
Article
Chemistry, Analytical
Xi Chen, Shuli Tang, Dallas Freitas, Erin Hirtzel, Heyong Cheng, Xin Yan
Summary: This study presents a novel method for the characterization of phosphatidylcholine isomers using Mn(II)-catalyzed epoxidation. The method allows for the simultaneous identification of carbon-carbon double bond and stereonumbering positional isomers. The bifunctional derivatization takes place in seconds and produces clear and interpretable diagnostic ions.
Article
Chemistry, Multidisciplinary
Dacheng Kuai, Heyong Cheng, Kai-Yuan Kuan, Xin Yan
Summary: The study demonstrates that acceleration of a five-component spiro-pyrrolidine construction can be achieved in microdroplets and thin films, with deposition method and mild heating being crucial factors for product formation. Three key intermediates were identified by mass spectrometry to elucidate the tandem reaction mechanism. Additionally, hydrogen bonding was found to significantly reduce the energy barrier at the air-liquid interface.
CHEMICAL COMMUNICATIONS
(2021)
