• Title/Summary/Keyword: Laser-desorption

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Matrix-Assisted Variable Wavelength Laser Desorption Ionization of Peptides; Influence of the Matrix Absorption Coefficient on Expansion Cooling

  • Ahn, Sung-Hee;Bae, Yong-Jin;Kim, Myung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.9
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    • pp.2955-2960
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    • 2012
  • Product ion yields in the in- and post-source decays of three peptide ions, $[Y_5X+H]^+$ (X = Y (tyrosine), K (lysine), and R (arginine)), generated by matrix-assisted laser desorption ionization (MALDI) were measured at six wavelengths, 307, 317, 327, 337, 347, and 357 nm, using ${\alpha}$-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) as the matrices. The temperatures of the early and late plumes generated by MALDI were estimated via kinetic analysis of the product ion yield data. For both matrices, the temperature drop (${\Delta}T$), i.e. the difference in the temperature between the early and late plumes, displayed negative correlation with the absorption coefficient. This was in agreement with the previous reasoning that deeper laser penetration and larger amount of material ablation arising from smaller absorption coefficient would result in larger extent of expansion cooling. The results support the postulation of the expansion cooling occurring in the plume presented previously.

Focused Electrospray Deposition for Matrix-assisted Laser Desorption/Ionization Mass Spectrometry

  • Jeong, Kyung-Hwan;Seo, Jong-Cheol;Yoon, Hye-Joo;Shin, Seung-Koo
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2293-2298
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    • 2010
  • Focused electrospray (FES) deposition method is presented for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. FES ion optics consists of two cylindrical focusing electrodes capped with a truncated conical electrode through which an electrospray emitter passes along the cylindrical axis. A spray of charged droplets is focused onto a sample well on a MALDI target plate under atmospheric pressure. The shape and size distributions of matrix crystals are visualized by scanning electron microscope and the mass spectra are obtained by time-of-flight mass spectrometry. Angiotensin II, bradykinin, and substance P are used as test samples, while $\alpha$-cyano-4-hydroxycinnamic acid and dihydroxybenzoic acid are employed as matrices. FES of a sample/matrix mixture produces fine crystal grains on a 1-3 mm spot and reproducibly yields the mass spectra with little shot-to-shot and spot-to-spot variations. Although FES greatly stabilizes the signals, the space charge due to matrix ions limits the detection sensitivity of peptides. To avoid the space charge problem, we adopted a dual FES/FES mode, which separately deposits matrix and sample by FES in sequence. The dual FES/FES mode reaches the detection sensitivity of 0.88 amol, enabling ultrasensitive of peptides by homogeneously depositing matrix and sample under atmospheric pressure.

Novel analysis procedure for red ginseng polysaccharides by matrix-assisted laser desorption/ionization time-of-flight/time-offlight mass spectrometry

  • Jin, Ye Rin;Oh, Myung Jin;Yuk, Heung Joo;An, Hyun Joo;Kim, Dong Seon
    • Journal of Ginseng Research
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    • v.45 no.5
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    • pp.539-545
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    • 2021
  • Background: Red ginseng polysaccharides (RGPs) have been acknowledged for their outstanding immunomodulation and anti-tumor activities. However, their studies are still limited by the complexity of their structural features, the absence of purification and enrichment methods, and the rarity of the analytical instruments that apply to the analysis of such macromolecules. Thus, this study is an attempt to establish a new mass spectrometry (MS)-based analysis procedure for RGPs. Methods: Saponin pre-excluded powder of RG (RG-SPEP, 10 mg) was treated with 200 µL of distilled water and centrifuged for 5 h at 1000 rpm and 85 ℃. Ethanol-based precipitation and centrifugation were applied to obtain RGPs from the heated extracts. Further, endo-carbohydrase treatments were performed to produce specific saccharide fragments. Solid-phase extraction (SPE) processes were implemented to purify and enrich the enzyme-treated RGPs, while matrix-assisted laser desorption/ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) MS was employed for the partial structural analysis of the obtained RGPs. Results: Utilizing cellulase, porous graphitized carbon (PGC), hydrophilic interaction chromatography (HILIC), and MALDI-TOF/TOF MS, the neutral and acidic RGPs were qualitatively analyzed. Hexn and Hexn-18 (cellulose analogs) were determined to be novel neutral RGPs. Additionally, the [Unknown + Hexn] species were also determined as new acidic RGPs. Furthermore, HexAn (H) was determined as another form of the acidic RGPs. Conclusion: Compared to the previous methods of analysis, these unprecedented applications of HILIC-SPE and MALDI-TOF/TOF MS to analyze RGPs proved to be fairly effective for fractionating and detecting neutral and acidic components. This new procedure exhibits great potential as a specific tool for searching and determining various polysaccharides in many herbal medicines.

Studies of the Organic Molecules Dissociative Surface Ionization in the Mass-Spectrometric Surface Ionization Method

  • Ilkhomjan Saydumarov;Dilshadbek Usmanov
    • Mass Spectrometry Letters
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    • v.15 no.1
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    • pp.54-61
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    • 2024
  • An improved voltage modulation method (VMM) was used to control the heat release and adsorption properties of the adsorbent. In this work, the voltage and flux modulation methods were considered under unified experimental conditions of dissociative surface ionization (SI) of polyatomic organic molecules, the criteria were found when under VMM conditions the current relaxation of SI carries information about the kinetic properties of thermal desorption of ionizable dissociation particles arriving on the surface of polyatomic molecules. Conditions were found under which the relaxation of the ionic current in the flux modulation method is determined by the kinetics of the heterogeneous dissociation reaction of the original polyatomic molecules. The values of the thermal desorption rate constant K+ and the activation energy E+ obtained with VMM for desorption of (CH3)2NCH+2 ions with m/z 58 by adsorption of imipramine and amitriptyline molecules agree well with each other and with the results for the desorption of the same ions by adsorption of other molecules. This confirms one of the basic conditions for the equilibrium process SI - the a degree (β coefficient) of the same particles SI on the same emitter surface is the same and does not depend on the way these particles are formed on the emitter surface.

Laser-Direct Patterning of Nanostructured Metal Thin Films (나노구조 금속 박막의 레이저 직접 패터닝에 관한 연구)

  • Shin, Hyunkwon;Lee, Hyeongjae;Yoo, Hyeonggeun;Lim, Ki-Soo;Lee, Myeongkyu
    • Korean Journal of Metals and Materials
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    • v.48 no.2
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    • pp.163-168
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    • 2010
  • We here describe the laser-direct patterning of nanostructured metal thin films. This method involves light-matter interaction in which a pulsed laser beam impinging on the film generates a thermoelastic force that plays a role to detach the film from the substrate or underlying layers. A moderate cohesion of the nanostructured film enables localized desorption of the material upon irradiation by a spatiallymodulated laser beam, giving good fidelity with the transfered pattern. This photoresist-free process provides a simple high-resolution scheme for patterning metal thin films.

Discrimination of Bacillus anthracis Spores by Direct in-situ Analysis of Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight Mass Spectrometry

  • Jeong, Young-Su;Lee, Jonghee;Kim, Seong-Joo
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2635-2639
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    • 2013
  • The rapid and accurate identification of biological agents is a critical step in the case of bio-terror and biological warfare attacks. Recently, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been widely used for the identification of microorganisms. In this study, we describe a method for the rapid and accurate discrimination of Bacillus anthracis spores using MALDI-TOF MS. Our direct in-situ analysis of MALDI-TOF MS does not involve subsequent high-resolution mass analyses and sample preparation steps. This method allowed the detection of species-specific biomarkers from each Bacillus spores. Especially, B. anthracis spores had specific biomarker peaks at 2503, 3089, 3376, 6684, 6698, 6753, and 6840 m/z. Cluster and PCA analyses of the mass spectra of Bacillus spores revealed distinctively separated clusters and within-groups similarity. Therefore, we believe that this method is effective in the real-time identification of biological warfare agents such as B. anthracis as well as other microorganisms in the field.

Proteome Analysis of Waito-c Rice Seedlings Treated with Culture Fluid of Gibberellin-producing Fungus, Fusarium proliferatum KGL0401

  • Rim, Soon-Ok;Lee, Jin-Hyung;Hwang, Seon-Kap;Suh, Seok-Jong;Lee, Jin-Man;Rhee, In-Koo;Kim, Jong-Guk
    • Journal of Microbiology and Biotechnology
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    • v.16 no.12
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    • pp.1990-1994
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    • 2006
  • Fusarium proliferatum KGL0401 was previously isolated from Physalis alkekengi var. francheti plant roots and exhibited a high GA productivity. A gas chromatography-mass spectrometry (GC-MS) analysis of extracts of the culture fluid of F proliferatum KGL0401 also revealed the presence of $GA_1$, $GA_3$, $GA_4$, $GA_7$, $GA_{20}$, and $GA_{24}$. Therefore, the present study conducted a proteome analysis of waito-c rice treated with the culture fluid of the isolated F proliferatum KGL0401 to identify the protein expression triggered by the GA-containing culture fluid. The results revealed the overexpression of 180 protein spots in the sample treated with the culture fluid. Among them, 75 induced proteins were selected and analyzed by MALDI-TOF (matrix-assisted laser desorption-iorrization time-of-flight) mass spectrometry, followed by database searching, and 51 proteins were identified.