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At least 325 records · Page 18

Electrospray Generated from the Tip-Sealed Fine Glass Capillary Inserted with an Acupuncture Needle Electrode

In electrospray, excess charges are supplied to a sample solution by the occurrence of electrochemical reactions. Recently, different versions of electrospray, e.g., dielectric barrier electrospray ionization, inductive desorption electrospray ionization, and electrostatic-ionization driven by dielectric polarization, have been reported in which the sample solution was not in direct contact with the metal electrode but separated by dielectric materials. The objective of the current work is to elucidate the mechanism of dielectric barrier electrospray. A sealed borosilicate glass capillary inserted with a fine acupuncture needle was used as a probe. A sample solution (~ 400 nL) was captured on the glass capillary tip and a positive high voltage (HV) pulse (+ 4.5 kV) was applied to the internal metal electrode. Mass spectra were measured as a function of the HV pulse width from μs to 10 s. Ions started to be detected with the pulse width of ~ 5 ms. The ion intensities increased slowly with time and reached a plateau in a few seconds. The charge distribution of cytochrome c [M + nH]{sup n+} shifted to higher n values from a few ms to seconds. In addition to cone-jet mode normal electrospray that lasted until all the liquid sample was depleted from the glass tip, the polarization-induced electrospray ionization was observed at the early stage of the HV application. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Evolution of Interstellar Dust into Planetary Materials

Comets are believed to retain some interstellar materials, stored in fairly pristine conditions since-their formation. The composition and properties of cometary dust grains should reflect those of grains in the outer part of the protosolar nebula which, at least in part, were inherited from the presolar molecular cloud. However, infrared emission features in comets differ from their interstellar counterparts. These differences imply processing of interstellar material on its way to incorporation in comets, but C and N appear to be retained. Overall dust evolution from the interstellar medium (ISM) to planetary materials is accompanied by an increase in proportion of complex organics and a decrease in pure carbon phases. The composition of cometary dust grains was measured in situ during fly-by missions to comet Halley in 1986. The mass spectra of about 5000 cometary dust grains with masses of 5 x 10(exp -17) - 5 x 10(exp -12) g provide data about the presence and relative abundances of the major elements H, C, N, O,Na, Mg, Al, Si, S, Cl, K, Ca, Ti, Cr, Fe, Ni. The bulk abundances of major rock-forming elements integrated over all spectra were found to be solar within a factor of 2, while the volatile elements H, C, N, O in dust are depleted in respect to their total cosmic abundances. The abundances of C and N in comet dust are much closer to interstellar than to meteoritic and are higher than those of dust in the diffuse ISM. In dense molecular clouds dust grains are covered by icy mantles, the average composition of which is estimated to be H:C:N:O = 96:14:1:34. Up to 40% of elemental C and O may be sequestered in mantles. If we use this upper limit to add H, C, N and O as icy mantle material to the abundances residing in dust in the diffuse ISM, then the resulting values for H. C, and N match cometary abundances. Thus, ice mantles undergoing chemical evolution on grains in the dense ISM appear to have been transformed into less volatile and more complex organic residues wherein the H, C and N are largely retained and ultimately accreted in cometary dust. The abundance of O is about the same for cometary dust, meteorites and interstellar dust. In all these samples, most of O in a solid phase is bonded to silicates. In dense molecular clouds, the abundance of O in dust+mantles is significantly higher then in cometary dust. This difference may reflect the greater lability of oxygenated species toward astrophysical processing. Laboratory studies show that O-bearing functional groups in organic compounds tend to be relatively easily removed by heating and/or UV and particle irradiation . In Halley's coma, O-containing organic grains, being unstable, were located closest to the nucleus. The decomposition of the organic grain component in the coma provided a significant extended source contribution to O-containing gaseous species such as CO and H2CO.

Fomenkova, M. N.↗

Large Improvements in MS/MS Based Peptide Identification Rates using a Hybrid Analysis

We have developed a hybrid method for identifying peptides from global proteomics studies that significantly increases sensitivity and specificity in matching peptides to tandem mass spectra using database searches. The method increased the number of spectra that can be assigned to a peptide in a global proteomics study by 57-147% at an estimated false discovery rate of 5%, with clear room for even greater improvements. The approach combines the general utility of using consensus model spectra typical of database search methods1-3 with the accuracy of the intensity information contained in spectral libraries4-6. This hybrid approach is made possible by recent developments that elucidated the statistical framework common to both data analysis and statistical thermodynamics, resulting in a chemically inspired approach to incorporating fragment intensity information into both database searches and spectral library searches. We applied this approach to proteomics analysis of Synechococcus sp. PCC 7002, a cyanobacterium that is a model organism for studies of photosynthetic carbon fixation and biofuels development. The increased specificity and sensitivity of this approach allowed us to identify many more peptides involved in the processes important for photoautotrophic growth.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Photodissociation of protonated leucine-enkephalin in the VUV range of 8-40 eV

Until now, photodissociation studies on free complex protonated peptides were limited to the UV wavelength range accessible by intense lasers. We have studied photodissociation of gas-phase protonated leucine-enkephalin cations for vacuum ultraviolet (VUV) photons energies ranging from 8 to 40 eV. We report time-of-flight mass spectra of the photofragments and various photofragment-yields as a function of photon energy. For sub-ionization energies our results are in line with existing studies on UV photodissociation of leucine-enkephalin. For photon energies exceeding 10 eV we could identify a new dissociation scheme in which photoabsorption leads to a fast loss of the tyrosine side chain. This loss process leads to the formation of a residual peptide that is remarkably cold internally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Newly observed D(2550), D(2610), and D(2760) as 2S and 1D charmed mesons

We study three charmed resonances, D(2550), D(2610), and D(2760), newly observed by the BABAR Collaboration, utilizing the mass spectra and investigating the strong decays. Our calculation indicates that D(2610) is an admixture of 2{sup 3}S{sub 1} and 1{sup 3}D{sub 1} with J{sup P}=1{sup -}. D(2760) can be explained as either the orthogonal partner of D(2610) or 1{sup 3}D{sub 3}. Our estimate of the decay width for D(2550), assuming it as 2{sup 1}S{sub 0}, is far below the experimental value. The decay behavior of the remaining two 1D charmed mesons, i.e., {sup 3}D{sub 2} and {sup 1}D{sub 2} (J{sup P}=2{sup -}) states, is predicted, which will help future experimental search for these missing D-wave charmed mesons.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

BH-DFTB/DFT calculations for iron clusters

We present a study on the structural, electronic, and magnetic properties of Fe{sub n}(n = 2 − 20) clusters by performing density functional tight binding (DFTB) calculations within a basin hopping (BH) global optimization search followed by density functional theory (DFT) investigations. The structures, total energies and total spin magnetic moments are calculated and compared with previously reported theoretical and experimental results. Two basis sets SDD with ECP and 6-31G** are employed in the DFT calculations together with BLYP GGA exchange-correlation functional. The results indicate that the offered BH-DFTB/DFT strategy collects all the global minima of which different minima have been reported in the previous studies by different groups. Small Fe clusters have three kinds of packing; icosahedral (Fe{sub 9−13}), centered hexagonal antiprism (Fe{sub 14−17}, Fe{sub 20}), and truncated decahedral (Fe{sub 17(2)}, Fe{sub 18−19}). It is obtained in a qualitative agreement with the time of flight mass spectra that the magic numbers for the small Fe clusters are 7, 13, 15, and 19 and with the collision induced dissociation experiments that the sizes 6, 7, 13, 15, and 19 are thermodynamically more stable than their neighboring sizes. The spin magnetic moment per atom of Fe{sub n}(n = 2 − 20) clusters is between 2.4 and 3.6 μ{sub B} for the most of the sizes. The antiferromagnetic coupling between the central and the surface atoms of the Fe{sub 13} icosahedron, which have already been reported by experimental and theoretical studies, is verified by our calculations as well. The quantitative disagreements between the calculations and measurements of the magnetic moments of the individual sizes are still to be resolved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Measurement of the D - s Decay Constant f Ds and Observation of New Charm Resonances Decaying to D*π

The absolute branching fractions for the decays D - s → ℓ-$\bar{v}$ - (ℓ = e, μ, or τ) are measured using a data sample corresponding to an integrated luminosity of 521 fb -1 collected at center of mass energies near 10.58 GeV with the BABAR detector at the PEPII e + e - collider at SLAC. The number of D s - mesons is determined by reconstructing the recoiling system DKXγ in events of the type e + e - → DKXD* s - , where D* s - → D s - γ and X represents additional pions from fragmentation. The D s - → ℓ - v ℓ events are detected by full or partial reconstruction of the recoiling system DKX{gamma}ℓ. The following results are obtained: β(D s - → μ - v) = (6.02 ± 0.38 ± 0.34) x 10 -3 , {Beta}(D s - → τ - v) = (5.00 ± 0.35 ± 0.49) x 10 -2 , and B(D s - → e - ν) < 2.8 x 10 -4 at 90% C.L., where the first uncertainty is statistical and the second is systematic. The branching fraction measurements are combined to determine the D s - decay constant f Ds = (258.6 ± 6.4 ± 7.5) MeV. In addition, a study has been performed of the D + π} - , D 0 π} + , and D* + π - systems in inclusive e + e - → c c interactions in a search for excited D meson states. The dataset used consists of {approx}454 fb -1 . The mass spectra for these systems show, for the first time, candidates for the radial excitations of the D 0 , D* 0 , and D* + , as well as the L = 2 excited states of the D 0 and D - , where L is the orbital angular momentum of the quarks. Finally, a prototype of a next generation Detector of Internally Reflected Cherenkov radiation (Focusing DIRC) has been tested using a 10 GeV electron beam at SLAC. The Focusing DIRC is based on the DIRC which was used in the BABAR detector, but has new pixel photon detectors which improve the resolution on the single photon time of propagation by about an order of magnitude allowing, for the first time, to correct the chromatic smearing in the Cherenkov angle. The Focusing DIRC may be used in a future Super-B factory.

43 PARTICLE ACCELERATORS↗

Laser Pulse Width Dependence and Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization

Ultraviolet laser pulses at 355 nm with variable pulse widths in the region from 170 ps to 1.5 ns were used to investigate the ionization mechanism of matrix-assisted laser desorption/ionization (MALDI) for matrices 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and sinapinic acid (SA). The mass spectra of desorbed ions and the intensity and velocity distribution of desorbed neutrals were measured simultaneously for each laser shot. These quantities were found to be independent of the laser pulse width. A comparison of the experimental measurements and numerical simulations according to the multiphoton ionization, coupled photophysical and chemical dynamics (CPCD), and thermally induced proton transfer models showed that the predictions of thermally induced proton transfer model were in agreement with the experimental data, but those of the multiphoton ionization model were not. Moreover, the predictions of the CPCD model based on singlet–singlet energy pooling were inconsistent with the experimental data of CHCA and SA, but were consistent with the experimental data of DHB only when some parameters used in the model were adjusted to extreme values. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Quasiclassical theory of the Dirac equation with a scalar-vector interaction and its applications in the physics of heavy-light mesons

We construct a relativistic potential quark model of D, D{sub s}, B, and B{sub s} mesons in which the light quark motion is described by the Dirac equation with a scalar-vector interaction and the heavy quark is considered a local source of the gluon field. The effective interquark interaction is described by a combination of the perturbative one-gluon exchange potential V{sub Coul}(r)=-{xi}/r and the long-range Lorentz-scalar and Lorentz-vector linear potentials S{sub l.r.}(r)=(1-{lambda})({sigma}r+V{sub 0}) and V{sub l.r.}(r)={lambda}({sigma}r+V{sub 0}), where 0{<=}{lambda}<1/2. Within the quasiclassical approximation, we obtain simple asymptotic formulas for the energy and mass spectra and for the mean radii of D, D{sub s}, B, and B{sub s} mesons, which ensure a high accuracy of calculations even for states with the radial quantum number n{sub r{approx}}1. We show that the fine structure of P-wave states in heavy-light mesons is primarily sensitive to the choice of two parameters: the strong-coupling constant {alpha}{sub s} and the coefficient {lambda} of mixing of the long-range scalar and vector potentials S{sub l.r.}(r) and V{sub l.r.}(r). The quasiclassical formulas for asymptotic coefficients of wave functions at zero and infinity are obtained.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Study of jets produced in association with a W boson in pp collisions at root s=7 TeV with the ATLAS detector

We report a study of final states containing a W boson and hadronic jets, produced in proton-proton collisions at a center-of-mass energy of 7 TeV. The data were collected with the ATLAS detector at the CERN LHC and comprise the full 2010 data sample of 36 pb{sup -1}. Cross sections are determined using both the electron and muon decay modes of the W boson and are presented as a function of inclusive jet multiplicity, N{sub jet}, for up to five jets. At each multiplicity, cross sections are presented as a function of jet transverse momentum, the scalar sum of the transverse momenta of the charged lepton, missing transverse momentum, and all jets, the invariant mass spectra of jets, and the rapidity distributions of various combinations of leptons and final-state jets. The results, corrected for all detector effects and for all backgrounds such as diboson and top quark pair production, are compared with particle-level predictions from perturbative QCD. Leading-order multiparton event generators, normalized to the next-to-next-to-leading-order total cross section for inclusive W-boson production, describe the data reasonably well for all measured inclusive jet multiplicities. Next-to-leading-order calculations from MCFM, studied here for N{sub jet} {le} 2, and BlackHat-Sherpa, studied here for N{sub jet} {le} 4, are found to be mostly in good agreement with the data.

43 PARTICLE ACCELERATORS↗

Quantitative Collision Cross-Sections from FTICR Linewidth Measurements: Improvements in Theory and Experiment

Two corrections to the equation used in the cross-sectional areas by Fourier transform ion cyclotron resonance (“CRAFTI”) technique are identified. In CRAFTI, ion collision cross-sections are obtained from the pressure-dependent ion linewidths in Fourier transform mass spectra. The effects of these corrections on the accuracy of the cross-sections obtained using the CRAFTI technique are evaluated experimentally using the 20 biogenic amino acids and several crown ether complexes with protonated alkyl monoamines. Good absolute agreement is obtained between the CRAFTI cross-sections and the corresponding cross-sections obtained using both static drift ion mobility spectrometry and computational simulations. These results indicate that the CRAFTI cross-sections obtained using the updated equation presented here are quantitatively descriptive of the size and shape of the gas-phase ions. Cross-sections that differ by less than 3% are measured for the isobaric isomers n-butylamine and tert-butylamine complexed with the crown ethers. This level of precision is similar to what has been achieved previously using traveling wave ion mobility devices. These results indicate that CRAFTI can be used to probe subtle structural differences between ions with approximately the same precision as that achieved in traveling wave ion mobility devices. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Unimolecular dissociation of anthracene and acridine cations: The importance of isomerization barriers for the C{sub 2}H{sub 2} loss and HCN loss channels

The loss of C{sub 2}H{sub 2} is a low activation energy dissociation channel for anthracene (C{sub 14}H{sub 10}) and acridine (C{sub 13}H{sub 9}N) cations. For the latter ion another prominent fragmentation pathway is the loss of HCN. We have studied these two dissociation channels by collision induced dissociation experiments of 50 keV anthracene cations and protonated acridine, both produced by electrospray ionization, in collisions with a neutral xenon target. In addition, we have carried out density functional theory calculations on possible reaction pathways for the loss of C{sub 2}H{sub 2} and HCN. The mass spectra display features of multi-step processes, and for protonated acridine the dominant first step process is the loss of a hydrogen from the N site, which then leads to C{sub 2}H{sub 2}/HCN loss from the acridine cation. With our calculations we have identified three pathways for the loss of C{sub 2}H{sub 2} from the anthracene cation, with three different cationic products: 2-ethynylnaphthalene, biphenylene, and acenaphthylene. The third product is the one with the overall lowest dissociation energy barrier. For the acridine cation our calculated pathway for the loss of C{sub 2}H{sub 2} leads to the 3-ethynylquinoline cation, and the loss of HCN leads to the biphenylene cation. Isomerization plays an important role in the formation of the non-ethynyl containing products. All calculated fragmentation pathways should be accessible in the present experiment due to substantial energy deposition in the collisions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bulk matter fields on a GRS-inspired braneworld

In this paper we investigate the localization and mass spectra of bulk matter fields on a Gergory-Rubakov-Sibiryakov-inspired braneworld. In this braneworld model, there are one thick brane located at the origin of the extra dimension and two thin branes at two sides. For spin 1/2 fermions coupled with the background scalar φ via η Ψ-bar φ{sup p}Ψ with p a positive odd integer, the zero mode of left-hand fermions can be localized on the thick brane for finite distance of the two thin branes, and there exist some massive bound modes and resonance modes. The resonances correspond to the quasi-localized massive fermions. For free massless spin 0 scalars, the zero mode can not be localized on the thick brane when the two thin branes are located finitely. While for a massive scalar Φ coupled with itself and the background scalar field φ, in order to get a localized zero mode on the thick brane, a fine-tuning relation should be introduced. Some massive bound modes and resonances also will appear. For spin 1 vectors, there is no bound KK mode because the effective potential felt by vectors vanishes outside the two thin branes. We also investigate the physics when the distance of the two thin branes tends to infinity.

79 ASTRONOMY AND ASTROPHYSICS↗

Machine Learning Correlation of Electron Micrographs and ToF-SIMS for the Analysis of Organic Biomarkers in Mudstone

The spatial distribution of organics in geological samples can be used to determine when and how these organics were incorporated into the host rock. Mass spectrometry (MS) imaging can rapidly collect a large amount of data, but ions produced are mixed without discrimination, resulting in complex mass spectra that can be difficult to interpret. Here, we apply unsupervised and supervised machine learning (ML) to help interpret spectra from time-of-flight-secondary ion mass spectrometry (ToF-SIMS) of an organic-carbon-rich mudstone of the Middle Jurassic of England (UK). It was previously shown that the presence of sterane molecular biomarkers in this sample can be detected via ToF-SIMS (Pasterski, M. J. et al., Astrobiology 2023, 23, 936). We use unsupervised ML on scanning electron microscopy–electron dispersive spectroscopy (SEM-EDS) measurements to define compositional categories based on differences in elemental abundances. We then test the ability of four ML algorithms─k-nearest neighbors (KNN), recursive partitioning and regressive trees (RPART), eXtreme gradient boost (XGBoost), and random forest (RF)─to classify the ToF-SIM spectra using (1) the categories assigned via SEM-EDS, (2) organic and inorganic labels assigned via SEM-EDS, and (3) the presence or absence of detectable steranes in ToF-SIMS spectra. In terms of predictive accuracy and balanced accuracy, KNN was the best performing model and RPART the worst. The feature importance, or the specific features of the ToF-SIM spectra used by the models to make classifications, cannot be determined for KNN, preventing posthoc model interpretation. Nevertheless, the feature importance extracted from the other models was useful for interpreting spectra. In conclusion, we determined that some of the organic ions used to classify biomarker containing spectra may be fragment ions derived from kerogen which is abundant in this mudstone sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Assemblies, Genes and Genomics Integrated Efficiently (MAGGIE)

Final report on MAGGIE. We set ambitious goals to model the functions of individual organisms and their community from molecular to systems scale. These scientific goals are driving the development of sophisticated algorithms to analyze large amounts of experimental measurements made using high throughput technologies to explain and predict how the environment influences biological function at multiple scales and how the microbial systems in turn modify the environment. By experimentally evaluating predictions made using these models we will test the degree to which our quantitative multiscale understanding wilt help to rationally steer individual microbes and their communities towards specific tasks. Towards this end we have made substantial progress towards understanding evolution of gene families, transcriptional structures, detailed structures of keystone molecular assemblies (proteins and complexes), protein interactions, biological networks, microbial interactions, and community structure. Using comparative analysis we have tracked the evolutionary history of gene functions to understand how novel functions evolve. One level up, we have used proteomics data, high-resolution genome tiling microarrays, and 5' RNA sequencing to revise genome annotations, discover new genes including ncRNAs, and map dynamically changing operon structures of five model organisms: For Desulfovibrio vulgaris Hildenborough, Pyrococcus furiosis, Sulfolobus solfataricus, Methanococcus maripaludis and Haiobacterium salinarum NROL We have developed machine learning algorithms to accurately identify protein interactions at a near-zero false positive rate from noisy data generated using tagfess complex purification, TAP purification, and analysis of membrane complexes. Combining other genome-scale datasets produced by ENIGMA (in particular, microarray data) and available from literature we have been able to achieve a true positive rate as high as 65% at almost zero false positives when applied to the manually curated training set. Applying this method to the data representing around a quarter of the fraction space for water soluble proteins in D. vulgaris, we obtained 854 reliable pair wise interactions. Further, we have developed algorithms to analyze and assign significance to protein interaction data from bait pull-down experiments and integrate these data with other systems biology data through associative biclustering in a parallel computing environment. We will 'fill-in' missing information in these interaction data using a 'Transitive Closure' algorithm and subsequently use 'Between Commonality Decomposition' algorithm to discover complexes within these large graphs of protein interactions. To characterize the metabolic activities of proteins and their complexes we are developing algorithms to deconvolute pure mass spectra, estimate chemical formula for m/z values, and fit isotopic fine structure to metabolomics data. We have discovered that in comparison to isotopic pattern fitting methods restricting the chemical formula by these two dimensions actually facilitates unique solutions for chemical formula generators. To understand how microbial functions are regulated we have developed complementary algorithms for reconstructing gene regulatory networks (GRNs). Whereas the network inference algorithms cMonkey and Inferelator developed enable de novo reconstruction of predictive models for GRNs from diverse systems biology data, the RegPrecise and RegPredict framework developed uses evolutionary comparisons of genomes from closely related organisms to reconstruct conserved regulons. We have integrated the two complementary algorithms to rapidly generate comprehensive models for gene regulation of understudied organisms. Our preliminary analyses of these reconstructed GRNs have revealed novel regulatory mechanisms and cis-regulatory motifs, as well asothers that are conserved across species. Finally, we are supporting scientific efforts in ENIGMA with data management solutions and by integrating all of the algorithms, software and data into a Knowledgebase. For instance, we have developed the RegPrecise database (http://regprecise.lbl.gov) which represents manually curated sets of regulons laying the basis for automatic annotation of regulatory interactions in closely related species. We are also in the midst of scaling up MicrobesOnline to handle the growing volume of sequence and functional genomics data. Over the last year our efforts have been focused on providing support for additional genomic and functional genomic data types. Similarly, we have developed several visualization tools to help with the exploration of complex systems biology datasets. A case in point is the Gaggle Genome Browser (GGB), which was enhanced with visualizations for plotting peptide detections and protein-DNA binding alongside transcriptome structure, plus the ability to interactively filter by signal intensity or p-value.

54 ENVIRONMENTAL SCIENCES↗

Dissociation of internal energy-selected methyl bromide ion revealed from threshold photoelectron-photoion coincidence velocity imaging

Dissociative photoionization of methyl bromide (CH{sub 3}Br) in an excitation energy range of 10.45–16.90 eV has been investigated by using threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. The coincident time-of-flight mass spectra indicate that the ground state X{sup 2}E of CH{sub 3}Br{sup +} is stable, and both A{sup 2}A{sub 1} and B{sup 2}E ionic excited states are fully dissociative to produce the unique fragment ion of CH{sub 3}{sup +}. From TPEPICO 3D time-sliced velocity images of CH{sub 3}{sup +} dissociated from specific state-selected CH{sub 3}Br{sup +} ion, kinetic energy release distribution (KERD) and angular distribution of CH{sub 3}{sup +} fragment ion are directly obtained. Both spin-orbit states of Br({sup 2}P) atom can be clearly observed in fast dissociation of CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion along C–Br rupture, while a KERD of Maxwell-Boltzmann profile is obtained in dissociation of CH{sub 3}Br{sup +}(B{sup 2}E) ion. With the aid of the re-calculated potential energy curves of CH{sub 3}Br{sup +} including spin-orbit coupling, dissociation mechanisms of CH{sub 3}Br{sup +} ion in A{sup 2}A{sub 1} and B{sup 2}E states along C–Br rupture are revealed. For CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion, the CH{sub 3}{sup +} + Br({sup 2}P{sub 1/2}) channel is occurred via an adiabatic dissociation by vibration, while the Br({sup 2}P{sub 3/2}) formation is through vibronic coupling to the high vibrational level of X{sup 2}E state followed by rapid dissociation. C–Br bond breaking of CH{sub 3}Br{sup +}(B{sup 2}E) ion can occur via slow internal conversion to the excited vibrational level of the lower electronic states and then dissociation.

74 ATOMIC AND MOLECULAR PHYSICS↗

Pollen Lipidomics: Lipid Profiling Exposes a Notable Diversity in 22 Allergenic Pollen and Potential Biomarkers of the Allergic Immune Response

Pollen grains are the male gametophytes that deliver sperm cells to female gametophytes during sexual reproduction of higher plants. Pollen is a major source of aeroallergens and environmental antigens. The pollen coat harbors a plethora of lipids that are required for pollen hydration, germination, and penetration of the stigma by pollen tubes. In addition to proteins, pollen displays a wide array of lipids that interact with the human immune system. Prior searches for pollen allergens have focused on the identification of intracellular allergenic proteins, but have largely overlooked much of the extracellular pollen matrix, a region where the majority of lipid molecules reside. Lipid antigens have attracted attention for their potent immunoregulatory effects. By being in close proximity to allergenic proteins on the pollen surface when they interact with host cells, lipids could modify the antigenic properties of proteins. We performed a comparative pollen lipid profiling of 22 commonly allergenic plant species by the use of gas chromatography-mass spectroscopy, followed by detailed data mining and statistical analysis. Three experiments compared pollen lipid profiles. We built a database library of the pollen lipids by matching acquired pollen-lipid mass spectra and retention times with the NIST/EPA/NIH mass-spectral library. We detected, identified, and relatively quantified more than 106 lipid molecular species including fatty acids, n-alkanes, fatty alcohols, and sterols. Pollen derived lipids stimulation up-regulate cytokines expression of dendritic and natural killer T cells co-culture. Here we report on a lipidomic analysis of pollen lipids that can serve as a database for identifying potential lipid antigens and/or novel candidate molecules involved in allergy. The database provides a resource that facilitates studies on the role of lipids in the immunopathogenesis of allergy. Pollen lipids vary greatly among allergenic species and contain many molecules that have stimulatory or regulatory effects on immune responses.

59 BASIC BIOLOGICAL SCIENCES↗