Mass spectrometric monitoring of ligand-bridged hot electron transfer and anaerobic oxidization on auto renewable droplet-based plasmonic nanoreactors under visible light illumination.

The light induced hot-electron on plasmonic nanostructures has been recognized as a breakthrough discovery for photovoltaic and photocatalytic applications. With mass spectrometry, we demonstrate the dynamics of hot electron transfers of anaerobic oxidization reactions on Au decorated TiO2 plasmonic nanoparticles, which were coated on the inner surface of a flask. Those nanoparticles were covered by continuously renewed liquid droplets of solvent and reactants that were transported through a Venturi jet mixer with auto-spray. In addition to intensive mass transfer in such droplet-based nanoreactors, as well as strong adsorption of reactants and rapid desorption of products on materials surfaces, the localized surface plasmon resonance (LSPR) excitation upon visible light illumination, by which accumulated energies of plasmons are transferred to electrons in the conduction band of the material, attributes to the efficient photocatalytic transformation. Mass spectrometric detection of intermediate radical anions and negative ions with stable isotope labeling unambiguously identifies that highly energetic hot electrons can escape from the plasmonic nanostructures, be collected by adsorbed molecules, and initiate bond cleavages. It was demonstrated that losses of two H atoms result in the anaerobic oxidization of each benzyl alcohol molecule to a benzyl aldehyde molecule in the absence of molecular oxygen with more than 90 % yields. The well recyclable plasmonic nanoreactors implicate the injection of transferred electrons eventually back to electronically depleted Au+ positive ions. Bridged by adsorbed molecules, electrons were repeatedly circulated back and forth in plasmonic nanoreactors, where the collected light was eventually converted into chemical energy.

Direct mass spectrometric imaging of document handwriting with laser desorption ionization and post ultraviolet photodissociation.

Handwriting represents personal education and physical or psychological states. This work describes a chemical imaging technique for document evaluation that combines laser desorption ionization with post ultraviolet photo-induced dissociation (LDI-UVPD) in mass spectrometry. Taken the advantages of chromophores in ink dyes, handwriting papers were subjected to direct laser desorption ionization without additional matrix materials. It is a surface-sensitive analytical method that uses a low intensity pulsed laser at 355 nm to remove chemical components from very outermost surfaces of overlapped handwritings. Meanwhile, the transfer of photoelectrons to those compounds leads to the ionization and the formation of radical anions. The gentle evaporation and ionization property enable the dissection of chronological orders. Paper documents maintain intact without extensive damages after laser irradiation. The evolving plume resulting from the irradiation of the 355 nm laser is fired by the second ultraviolet laser at 266 nm that is in parallel to the sample surface. In contrast to collision activated dissociation in tandem MS/MS, such post ultraviolet photodissociation generates much more different fragment ions through electron-directed specific cleavages of chemical bonds. LDI-UVPD can not only provide graphic representation of chemical components but also reveal hidden dynamic features such as alterations, pressures and aging.

GmABR1 encoding an ERF transcription factor enhances the tolerance to aluminum stress in Arabidopsis thaliana.

The ethylene response factor (ERF) transcription factors, which is one of the largest transcription factor families in plants, are involved in biological and abiotic stress response and play an important role in plant growth and development. In this study, the GmABR1 gene from the soybean inbred line Zhonghuang24 (ZH24)×Huaxia 3 (HX3) was investigated its aluminum (Al) tolerance. GmABR1 protein has a conserved domain AP2, which is located in the nucleus and has transcriptional activation ability. The results of real-time quantitative PCR (qRT-PCR) showed that the GmABR1 gene presented a constitutive expression pattern rich in the root tip, stem and leaf tissues of HX3. After Al stress, the GmABR1 transcript was significantly increased in the roots. The transcripts of GmABR1 in the roots of HX3 treated with 50 µM AlCl3 was 51 times than that of the control. The GmABR1 was spatiotemporally specific with the highest expression levels when Al concentration was 50 µM, which was about 36 times than that of the control. The results of hematoxylin staining showed that the root tips of GmABR1-overexpression lines were stained the lightest, followed by the control, and the root tips of GmABR1 RNAi lines were stained the darkest. The concentrations of Al3+ in root tips were 207.40 µg/g, 147.74 µg/g and 330.65 µg/g in wild type (WT), overexpressed lines and RNAi lines, respectively. When AlCl3 (pH4.5) concentration was 100 µM, all the roots of Arabidopsis were significantly inhibited. The taproot elongation of WT, GmABR1 transgenic lines was 69.6%, 85.6%, respectively. When treated with Al, the content of malondialdehyde (MDA) in leaves of WT increased to 3.03 µg/g, while that of transgenic Arabidopsis increased from 1.66-2.21 µg/g, which was lower than that of WT. Under the Al stress, the Al stress responsive genes such as AtALMT1 and AtMATE, and the genes related to ABA pathway such as AtABI1, AtRD22 and AtRD29A were up-regulated. The results indicated that GmABR1 may jointly regulate plant resistance to Al stress through genes related to Al stress response and ABA response pathways.

Imaging the Dynamics of Metal Ion-Coupled Electron Transfer on Material Surfaces with Redox/Photo Active Chelators.

Metal ions on surfaces of various materials as bulk matrices, doped structural units, or functionalized active sites play critical roles in the establishment of physical and chemical properties. Characterization of surface-bound metal ions and metal ion-coupled electron transfer are urgently needed for the determination of material structures as well as for understanding the relationship to macroscopic properties and technological applications. We present here a mass spectrometric (MS) technique that allows the monitoring of metal ion-coupled electron transfer along with spatial distributions, identities, quantities, valences, redox activities, and associated anions. It is based on the coordination of metal ions with chelators that are redox/photo active. Upon the irradiation of a focused laser beam, metal ions on material surfaces that are covered with chelators are evaporated, ionized, and detected with MS. This technique clearly reveals ligand-metal/metal-ligand and ligand-bridged electron transfers through MS or tandem MS/MS experiments. MS images of metal ions on material surfaces with the spatial resolution down to the sub-micrometer level have been obtained. It has been applied to the monitoring of hot electron transfer, leftover positive metal ions in localized surface plasmon resonance, and photocatalytic activities of crystalline facets of TiO2.

Plasmonic Hydroxyl Radical-Driven Epoxidation of Fatty Acid Double Bonds in Nanoseconds for On-Tissue Mass-Spectrometric Analysis and Bioimaging.

Lipids represent a large family of compounds with highly diverse structures that are involved in complex biological processes. A photocatalytic technique of on-tissue epoxidation of C=C double bonds has been developed for in situ mass spectrometric identification and spatial imaging of positional isomers of lipids. It is based on the plasmonic hot-electron transfer from irradiated gold nanowires to redox-active organic matrix compounds that undergo bond cleavages and generate hydroxyl radicals in nanoseconds. Intermediate radical anions and negative fragment ions have been unambiguously identified. Under the irradiation of a pulsed laser of the third harmonic of Nd3+:YAG (355 nm), the hydroxyl radical-driven epoxidation of unsaturated lipids with different numbers of C=C bonds can be completed in nanoseconds with high yields of up to 95%. Locations of C=C bonds were recognized with diagnostic fragment ions that were produced by either collision with an inert gas or auto-fragmentation resulting from the impact of energetic hot electrons and vibrational excitation. This technique has been applied to the analysis of breast cancer tissues of mice models without extensive sample processes. It was experimentally demonstrated that C=C bonds may be formed at different positions of not only regular mono- or poly-unsaturated fatty acids but also other odd-numbered long-chain fatty acids.

Metal-organic framework on porous TiO2 thin film-coated alumina beads for fractional distillation of plant essential oils.

Fractionation of essential oils is technically challenging due to enormous scaffold diversities and structural complexities as well as difficulties in the implementation of the fractionation in the gas phase. Packing beads with multi-dimensional hierarchical nanostructures have been developed herein to pack fractional columns for atmospheric distillations. Activated alumina beads were coated with a porous TiO2 thin film. Growth of Cu-BTC (benzene-1,3,5-tricarboxylate) crystals in resultant porous surfaces leads to the generation of new nanopores and increased metal centers for differential coordination with diverse components of essential oils. The TiO2 thin film is not only an integral part of the composites but also induces the oriented growth of Cu-BTC metal organic framework (MOF) crystals through coordinative interactions. These Al2O3@TiO2@Cu-BTC MOF beads show very strong absorptive capability for major components of essential oils, except for a single cyclic ether eucalyptol with steric hindrances. The eucalyptol was fractionated by using the column packed with those modified alumina beads from raw materials of Artemisia argyi, and Rosmarinus officinalis with high purities up to 96% and 93%, respectively.

Electrophoresis of Phosphoproteins on a Tandem Polymerized Gel.

A substrate with n phosphorylated sites may have 2n phosphor-forms for temporal-spatial regulation of biological events. Because phosphates do not significantly change molecular masses but net charges of proteins, those isoforms cannot be separated by regular mass-based sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE). A tandem polymerized gel was developed to resolve phosphor-isoforms with different masses, charges, and posttranslational modifications. Without the usage of SDS, the electrophoresis was primarily performed on three adjacent acidic polyacrylamide gels. After being concentrated on a stacking gel, protonated proteins were then separated on the Zr4+ immobilized gel through the coordination of metal ions with phosphates followed by further charge and mass (z/m)-based electrophoretic separation on a TiO2 containing gel. The presence of TiO2 nanoparticles in the third gel is aimed for the initiation of the polymerization of acrylamide in acidic conditions upon ultraviolet irradiation. Distinct isoforms of α-S1-casein, α-S2-casein, ß-casein, and κ casein model proteins located on 11, 8, 8, and 7 different bands of the tandem gel were unambiguously identified, respectively. With the tandem polymerized gel electrophoresis, new phosphorylation events that may occur simultaneously or sequentially were discovered in not only model proteins but also complex biological samples including human saliva, chicken egg, and sprouting maize. This provides a new tool to dissect complex biological processes that are triggered by dynamic phosphorylation events.

Cell-Based Ambient Venturi Autosampling and Matrix-Assisted Laser Desorption Ionization Mass Spectrometric Imaging of Secretory Products.

A cell-based ambient Venturi autosampling device was established for the monitoring of dynamic cell secretions in response to chemical stimulations in real time with temporal resolution on the order of a second. Detection of secretory products of cells and screening of bioactive compounds are primarily performed on an ambient autosampling probe and matrix-assisted laser desorption ionization (MALDI) mass spectrometry. It takes advantage of the Venturi effect in which the fluid flowing through an inlet capillary tube is automatically fed into a parallel array of multiple outlet capillaries. Cells are incubated inside the inlet capillary tube that is connected with either a syringe pump or liquid chromatography (LC) for the transfer of single compounds or mixtures, respectively. Secretory products were continuously pushed into the outlet capillaries and then spotted into a compressed thin film of the matrix material 9-aminoacridine for MALDI mass spectrometric imaging. In physiological pH, without the use of high voltages and without the use of chemical derivatizations, this platform can be applied to the direct assay of neurotransmitters or other secretory products released from cells in response to the stimulation of individual compounds or LC-separated eluates of natural mixtures. It provides a new way to identify bioactive compounds with a detection limit down to 0.04 fmol/pixel.

A Soft Evaporation and Ionization Technique for Mass Spectrometric Analysis and Bio-Imaging of Metal Ions in Plants Based on Metal-Iodide Cluster Ionization.

Protonation/deprotonation is the well-recognized mass spectrometric mechanism in matrix-assisted laser desorption ionization of organic molecules but not for metal ions with different oxidation states. We describe herein a soft evaporation and ionization technique for metal ions based on iodination/de-iodination in metal-iodide cluster ionization (MICI). It is not only able to determine identities and oxidation states of metal ions but also reveal spatial distributions and isotope ratios in response to physiological or environmental changes. A long chain alcohol 1-tetradecanol with no functional groups that can absorb laser irradiation was used to cover and prevent samples from direct laser ablation. Upon the irradiation of the third harmonic Nd3+:YAG (355 nm, 3 ns), iohexol containing three covalently bonded iodine atoms instantly generates negative iodide ions that can quantitatively form clusters with at least 14 essential metal ions present in plants. The detection limits vary with different metal ions down to low fmol. MICI eliminates the atomization process that obscures metal charges in inductively coupled plasma mass spectrometry. Because only metal ions can be iodinated with iohexol, interferences from the abundant organic molecules of plants that are confronted by secondary ion mass spectrometry (SIMS) are also greatly decreased.

Competing Deprotonation and Electron Capture Dissociation in MALDI Mass Spectrometry.

A protonation/deprotonation mechanism has been established for the interpretation of ions in MALDI. We show herein that negative ions can be generated in different ways. Molecules with different electron affinities have been spotted on surfaces of TiO2, ZnO, and a stainless steel plate for the investigation of electron capture dissociation in comparison with photo- or thermal-induced deprotonation upon irradiation of the third harmonic of Nd3+:YAG (355 nm) laser pulses. Detection of C60•- and Fe (II) (porph•-) radical anions unambiguously demonstrates the electron-transfer process and the exothermic capture of electrons. Radical anions of fatty acids were difficult to observe because of electron-directed ultrafast homolytic cleavage of O-H bonds unless there is a conjugated system as that in C60 and porphyrin for the delocalization and stabilization of acquired changes. The surface basicity of substrate materials was found to determine the competition of the electron-capture dissociation with deprotonation processes. Multiple electron transfers to pyrrole, -COOH, and Fe2+ of the heme were observed on TiO2 and the stainless steel plate but not on ZnO. When the heme was deprotonated by proton sponge 1,8-bis(dimethylamino)naphthalene, the occurrence of electron transfer on TiO2 was also not observed. It is proposed that negative charges of deprotonated ions prevent electron transfer due to the repulsive force. When both deprotonation and electron transfer are inhibited, adsorbed fatty acids on TiO2 undergo dehydration reactions to form titanium esters. In contrast, ZnO generates gaseous micelles composed of positive metal ions and negative fatty acid ions through either deprotonation or electron-capture dissociation.

Monitoring of adsorption and transfer of organochlorines in soybean seeds and sprouts with mass spectrometric imaging.

Development of analytical techniques that can monitor the adsorption, transfer and in-situ distribution of environmental pollutants in agricultural products is essential to ensure the implementation of stringent food safety standards for consumer protection. A mass spectrometric imaging approach is described herein to investigate the dynamic changes and spatial distributions of 4, 4'-DDT (dichlorodiphenyltrichloroethane) in soybean seeds and sprouts during the growth. Soy beans seeds incubated in DDT containing water were sliced in every 20 µm and directly blotted on the surface of a compressed thin film of (Bi2O3)0.07(CoO)0.03(ZnO)0.9 nanoparticles. Endogenous molecules and exogenous DDT compounds in soy bean seeds were ionized and dissociated by photoelectrons that are generated on surfaces of semiconductor nanoparticles upon the irradiation of the 3rd harmonic (355 nm) of Nd3+:YAG laser. Structural identification is achieved by the interpretation of fragment ions resulting from electron-initiated specific bond cleavages or hole oxidization. Mass spectrometric images reveal increased quantities of DDT residues in soy bean seeds and sprouts during the growth. It provides an in situ way without extensive sample preparation to monitor the transfer and distribution of exogenous pollutants as well as the possible impacts on plant growth.

Real-time laser induced chemical derivatizations of peptide N-Terminus for in-situ mass spectrometric sequencing at sub-picomole and nanosecond scale.

Distinguishing b- and y-ions is essential to compute amino acid sequences from either N- or C-terminus in mass spectrometry. We described herein a solvent free and real time on-plate derivatization approach that can tag N-terminus of peptides at microliter level with p-chlorobenzaldehyde or 2-hydroxy-5-methylisophthalaldehyde for matrix assisted laser desorption ionization mass spectrometry (MALDI MS). Less than 1 µL of sample solutions can be directly mixed with equal volumes of p-chlorobenzaldehyde or 2-hydroxy-5-methylisophthalaldehyde and α-cyano-4-hydroxycinnamic acid (CHCA), a matrix compound to co-crystalize with analytes for efficient absorption of laser energy and peptide ionization. When the mixture spotted on the sample plate is irradiated with the 3rd harmonic (355 nm) of Nd3+:YAG laser pulses (3 ns width), N-terminal amine groups of peptides instantly react with carbonyl groups of chlorobenzaldehyde or 2-hydroxy-5-methylisophthalaldehyde. Resultant peptides carrying with on-plate formed azomethine group (-CN-) are simultaneously protonated and isolated as precursor ions for subsequent collision-activated dissociation. The mass shift with unique Cl isotopic signature unambiguously distinguishes b ions from y ions and other ions. This method does not need extensive sample preparation and is useful for those samples with limited quantities down to sub-picomole level in sub-microliter volumes. The efficiency was demonstrated with synthetic peptides and tryptic peptides of model proteins. It was found that 2-hydroxy-5-methylisophthalaldehyde provides improved yield for peptides containing lysine residues. Unknown proteins of human saliva and bovine milk as well as phosphopeptides have been identified.

Mass spectrometric imaging reveals photocatalytic degradation intermediates of aromatic organochlorines resulting from interfacial photoelectron transfer and hydroxyl radical abstraction on semiconductor nanoparticles.

Organochlorines are highly persistent and toxic contaminants that are widely distributed and accumulated in various aquatic or soil environments as well as food chains. Heterogeneous photocatalytic degradation of such pollutants by using semiconductor nanoparticles has been recognized as one of the effective purification ways. Understanding of degradation mechanisms and designing of highly efficient semiconductor nanoparticles require structural identification of various degradation intermediates that are difficult to achieve with current spectroscopic techniques. Herein a mass spectrometric approach was developed to tackle interfacial photoelectron transfer and hydroxyl radical abstraction on different semiconductor nanoparticles. Chlorobenzenes (including hexachlorobenzene and chlorothalonil) adsorbed on the surfaces of nanoparticles were found to instantly undergo dechlorination and ring dissociation through photoelectron capture dissociation and abstraction of a chlorine atom from aromatic C-Cl bond by hydroxyl radicals. Different intermediates have been unambiguously identified with experimental evidences provided by a Q-TOF mass spectrometer. It has been demonstrated that both electron density around atoms and steric effects of side chains contribute to the site selectivity for photoelectron capture and hydroxyl radical abstraction. But the energies needed for chemical bond cleavages and the stabilization of acquired charges play important roles in degradation efficiency. By using mass spectrometric imaging, photocatalytic differences of different semiconductor nanoparticles have been revealed.

Electron Acceptive Mass Tag for Mass Spectrometric Imaging-Guided Synergistic Targeting to Mice Brain Glutamate Receptors.

Dysfunctional glutamate receptors (GluRs) have been implicated in neurological disorders and injuries. Hetero-tetrameric assemblies of different GluR subunits or splicing variants have distinct spatiotemporal expression patterns and pharmacological properties. Mass spectrometric imaging of GluRs-targeted small molecules is important for determining the regional preferences of these compounds. We report herein the development of a mass tag covalently bonded with glutamate or N-methyl-d-aspartate that functions as both an electron acceptor to generate mass spectrometric signals on irradiated (Bi2O3)0.07(CoO)0.03(ZnO)0.9 nanoparticles with the third harmonic (355 nm) of Nd3+:YAG laser and as the core component to target bilobed clamshell-like structures of GluRs. In this approach, different molecules produce the same tag ion. It provides a new avenue for quantitative assessment of spatial densities of different compounds, which cannot be achieved with well-established stable isotope labeling technique due to different ionization efficiency of different compounds. Various coexisting endogenous molecules are also simultaneously detected for investigation of overall physiological changes induced by these compounds. Because semiconductors do not generate background peaks, this method eliminates interferences from organic matrix materials that are used in regular MALDI (matrix assisted laser desorption ionization). The localized ionization provides high spatial resolution that can be down to sub-micrometers.

Ion fragmentations via photoelectron activated radical relays and competed hole oxidization on semiconductor nanoparticles for mass spectrometry.

Structural identification is challenging in mass spectrometric imaging because of inadequate sample quantities and limited sampling time in each pixel for tandem mass spectrometry (MS/MS) experiments, which are usually used for the generation of fragment ions. We report herein the observation of a cascade of highly specific chemical bond cleavages via a low-energy photoelectron activated radical relays and a competed hole oxidization on surfaces of (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles irradiated with the 3rd harmonic (355 nm) of the Nd3+: YAG laser. Distinguished from high energy electron impact (EI), this approach generates gaseous radical anions through the exothermic capture of low-energy tunneling electrons that are not able to cause extensive vibrational excitations. It was found not only original radical center but also secondary or even tertiary radical centers cause specific bond cleavages exclusively on α positions. The original radical center directly activates the cleavages of α-positioned chemical bonds that cause the formation of secondary radical centers. Ion fragmentations proceed along the newly formed radical centers that further activate the cleavages of their α-positioned chemical bonds. Using 8 compounds, we have demonstrated various radical reactions involved in desulfonation, cyclization, and ring contraction reactions as well as competed hole oxidization-generated hydroxyl radical substitution reactions. The interpretable fragment ions provide unambiguous experimental evidences for structural elucidation of drug residues and metabolites in mass spectrometric imaging of tissue slices without tandem mass spectrometry (MS/MS).

Mass spectrometric monitoring of interfacial photoelectron transfer and imaging of active crystalline facets of semiconductors.

Monitoring of interfacial electron transfer (ET) in situ is important to understand the ET mechanism and designing efficient photocatalysts. We describe herein a mass spectrometric approach to investigate the ultrafast transfer of photoelectrons that are generated by ultraviolet irradiation on surfaces of semiconductor nanoparticles or crystalline facets. The mass spectrometric approach can not only untargetedly detect various intermediates but also monitor their reactivity through associative or dissociative photoelectron capture dissociation, as well as electron detachment dissociation of adsorbed molecules. Proton-coupled electron transfer and proton-uncoupled electron transfer with radical initiated polymerization or hydroxyl radical abstraction have been unambiguously demonstrated with the mass spectrometric approach. Active crystalline facets of titanium dioxide for photocatalytic degradation of juglone and organochlorine dichlorodiphenyltrichloroethane are visualized with mass spectrometry imaging based on ion scanning and spectral reconstruction. This work provides a new technique for studying photo-electric properties of various materials.

Imaging of Endogenous Metabolites of Plant Leaves by Mass Spectrometry Based on Laser Activated Electron Tunneling.

A new mass spectrometric imaging approach based on laser activated electron tunneling (LAET) was described and applied to analysis of endogenous metabolites of plant leaves. LAET is an electron-directed soft ionization technique. Compressed thin films of semiconductor nanoparticles of bismuth cobalt zinc oxide were placed on the sample plate for proof-of-principle demonstration because they can not only absorb ultraviolet laser but also have high electron mobility. Upon laser irradiation, electrons are excited from valence bands to conduction bands. With appropriate kinetic energies, photoexcited electrons can tunnel away from the barrier and eventually be captured by charge deficient atoms present in neutral molecules. Resultant unpaired electron subsequently initiates specific chemical bond cleavage and generates ions that can be detected in negative ion mode of the mass spectrometer. LAET avoids the co-crystallization process of routinely used organic matrix materials with analyzes in MALDI (matrix assisted-laser desorption ionization) analysis. Thus uneven distribution of crystals with different sizes and shapes as well as background peaks in the low mass range resulting from matrix molecules is eliminated. Advantages of LAET imaging technique include not only improved spatial resolution but also photoelectron capture dissociation which produces predictable fragment ions.

Titanium Dioxide Photocatalytic Polymerization of Acrylamide for Gel Electrophoresis (TIPPAGE) of Proteins and Structural Identification by Mass Spectrometry.

Polyacrylamide gel electrophoresis (PAGE) coupled with mass spectrometry has been well established for separating, identifying and quantifying protein mixtures from cell lines, tissues or other biological samples. The copolymerization process of acrylamide and bis-acrylamide is the key to mastering this powerful technique. In general, this is a vinyl addition reaction initiated by free radical-generating reagents such as ammonium persulfate (APS) and tetramethylethylenediamine (TEMED) under basic pH and degassing experimental condition. We report herein a photocatalytic polymerization approach that is based on photo-generated hydroxyl radicals with nanoparticles of titanium dioxide. It was shown that the polymerization process is greatly accelerated in acidic condition when ultraviolet light shots on the gel solution containing TiO2 nanoparticles without degassing. This feature makes it very useful in preparing Triton X-100 acid urea (TAU) gel that has been developed for separating basic proteins such as histones and variants in acidic experimental condition. Additionally, the presence of titanium dioxide in the gel not only improves mechanistic property of gels but also changes the migration pattern of different proteins that have different affinities to titanium dioxide.

Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride.

A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O-H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves.

Laser Activated Electron Tunneling Based Mass Spectrometric Imaging of Molecular Architectures of Mouse Brain Revealing Regional Specific Lipids.

A comprehensive description of overall brain architecture at the molecular level is essential for understanding behavioral and cognitive processes in health and diseases. Although fluorescent labeling of target proteins has been successfully established to visualize a brain connectome, the molecular basis for diverse neurophysiological phenomena remains largely unknown. Here we report a brain-wide, molecular-level, and microscale imaging of endogenous metabolites, in particular, lipids of mouse brain by using laser activated electron tunneling (LAET) and mass spectrometry. In this approach, atomic electron emission along with finely tuned laser beam size provides high resolution that can be down to the sub-micrometer level to display spatial distribution of lipids in mouse brain slices. Electron-directed soft ionization has been achieved through exothermal capture of tunneling photoelectrons as well as unpaired electron-initiated chemical bond cleavages. Regionally specific lipids including saturated, mono-unsaturated, and poly-unsaturated fatty acids as well as other lipids, which may be implicated in neurological signaling pathways, have been discovered by using this laser activated electron tunneling based mass spectrometric imaging (LAET-MSI) technique.