Yuko Ichiyanagi

Nanoparticle-Assisted Laser Desorption/Ionization Based Mass Imaging with Cellular Resolution

Today, two-dimensional mass spectrometry analysis of biological tissues by means of a technique called mass imaging, mass spectrometry imaging (MSI), or imaging mass spectrometry (IMS) has found application in investigating the distribution of moleculesMSI with matrix-assisted laser desorption/ionization (MALDI) and secondary ion MS (SIMS). However, the size of the matrix crystal and the migration of analytes can decrease the spatial resolution in MALDI, and SIMS can only ionize compounds with relatively low molecular weights. To overcome these problems, we developed a nanoparticle-assisted laser desorption/ionization (nano-PALDI)-based MSI. We used nano-PALDI MSI to visualize lipids and peptides at a resolution of 15 microm in mammalian tissues.

Magnetic properties of NiO nanoparticles

Abstract NiO nanoparticles were produced by annealing Ni(OH)2 monolayer-nanoclusters above 973 K in air. Their diameters were estimated to be between 2 and 6 nm from X-ray diffraction patterns. In the magnetization measurements superparamagnetic or ferromagnetic behaviors were observed and characteristic properties of NiO nanoparticles were confirmed.

Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

Abstract We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm) and developed nanoparticle-assited laser desorption/ionization (nano-PALDI) mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da) without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-α-cinnamic acid (CHCA) and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

Structural, magnetic and thermal characterizations of Fe2O3 nanoparticle systems

X-ray, magnetic and differential thermal analysis and thermogravimetric (DTA-TG) measurements of Fe2O3 nanoparticles surrounded by amorphous SiO2were carried out. The mass loss above 370 K could be attributed to the dehydration. The broadened exothermic peak around 900 K was observed by the DTA analysis. Considering the results of the X-ray and magnetic analyses, this anomaly was interpreted as due to the g- to a-transition in the present Fe2O3nanoparticle system. The broadness of the peak and thus the gradual progress of the transformation would be attributed to the stress caused by the amorphous SiO2 network surrounding extremely small particles.

Synthesis of Gd2O3 nanoparticles for MRI contrast agents

Gd2O3 nanoparticles were synthesized by using our original method for application as MRI contrast agents. The sample diameters were controlled in the range 18–66 nm by adjusting the annealing temperature between 773 and 1273 K in air or in an Ar atmosphere. Magnetization measurements were performed at 300 K, and the effective magnetic moment of each sample was calculated. They showed paramagnetism at 300 K and they had large effective magnetic moment μeff of 7.15–8.05 μB. MRI measurements were performed in 0.8 wt% agarose solution, and the Gd2O3 nanoparticles were found to work as effective T1-shortening MRI contrast agents.

Comments on magnetically estimated Jc for MgB2 by critical state models

Abstract A reliable method is proposed for the estimation of J c eq ( H ) from irreversible magnetization data for a new type-II superconductor MgB 2 . In this case J c eq is the critical current density at the inner sample surface and H is the external field. The equation | J c ( H )|= ΔM ( H )/[ a {1− a /3 b }], often used for a 2 a ×2 b orthorhombic column geometry, is revealed to be incorrect near and below the full penetration field H p . Parameters obtained for the critical state suggest that flux bundle creeping is dominant in this superconductor.

Magnetic and Structural Studies of Ni(OH)2 Monolayered Nanoclusters

Chemical, magnetic and structural analysis have been carried out for the precipitates obtained by mixing NiCl26H2O and Na2SiO3 mH2O (m=0 or 9) aqueous solutions. The formation of Ni(OH)2 monolayered clusters with diameter of 2–3 nm was confirmed in the above precipitates. The exchange interaction in these Ni(OH)2 monolayered nanoclusters was also discussed on the basis of molecular field approximation.

Mass spectrometry imaging of the capsaicin localization in the capsicum fruits

We succeeded in performing mass spectrometry imaging (MSI) of the localization of capsaicin in cross-sections of the capsicum fruits at a resolution of 250 µm using matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. Post source decay of protonated capsaicin ion revealed structural information of the corresponding acid amide of vanillylamide and C 9 chain fatty acid. MALDI-TOF-MSI confirmed that localization of capsaicin in the placenta is higher than that in the pericarp. In addition, it revealed no localization of capsaicin in seed and the higher localization of capsaicin at placenta surface compared with that in the internal region. A quantitative difference was detected between localizations of capsaicin at placenta, pericarp and seed in the capsicum fruits. This imaging approach is a promising technique for rapid quality evaluation general food as well as health food and identification of medicinal capsaicin in plant tissues.

Oligonucleotide analysis by nanoparticle-assisted laser desorption/ionization mass spectrometry

We analyzed oligonucleotides by nanoparticle-assisted laser desorption/ionization (nano-PALDI) mass spectrometry (MS). To this end, we prepared several kinds of nanoparticles (Cr-, Fe-, Mn-, Co-based) and optimized the nano-PALDI MS method to analyze the oligonucleotides. Iron oxide nanoparticles with diammonium hydrogen citrate were found to serve as an effective ionization-assisting reagent in MS. The mass spectra showed both [M - H](-) and [M + xMe(2+)- H](-) (Me: transition metal) peaks. The number of metal-adducted ion signals depended on the length of the oligonucleotide. This phenomenon was only observed using bivalent metal core nanoparticles, not with any other valency metal core nanoparticles. Our pilot study demonstrated that iron oxide nanoparticles could easily ionize samples such as chemical drugs and peptides as well as oligonucleotides without the aid of an oligonucleotide-specific chemical matrix (e.g., 3-hydroxypicolinic acid) used in conventional MS methods. These results suggested that iron-based nanoparticles may serve as the assisting material of ionization for genes and other biomolecules.

Nanotrap and Mass Analysis of Aromatic Molecules by Phenyl Group-Modified Nanoparticle

To functionalize the surface of nanoparticles with phenyl groups for subsequent cross-linking with aromatic molecules by mutual interactions, we prepared functional nanoparticles (d = 3 nm) by silanization with phenyl-triethoxysilane. The nanoparticles had Fe(2)O(3) cores conjugated to phenyl groups; this was confirmed by Fourier transform infrared (FT-IR) spectroscopy and absorption spectrophotometry. The typical C-H and C-C peaks and the absorption at 240 nm, which corresponds to aromatic rings, were detected in the spectroscopic results for the phenyl group-modified nanoparticles. The nanoparticles could ionize aromatic (colchicine, reserpine, and bradykinin peptide) and nonaromatic (L-α-phosphatidylethanolamine,dioleoyl, and polyethylene glycol) molecules by nanoparticle-assisted laser desorption/ionization mass spectrometry. The nanoparticles worked as a selective trap and an ionization-assisting reagent in mass spectrometry for the aromatic molecular targets.