Journal of the Mass Spectrometry Society of Japan

REVIEWS

Miniaturized Time-of-Flight Mass Spectrometers for Bioagent Detection and Identification

Robert J. COTTER, Robert D. ENGLISH, Bettina WARSCHEID, Andy HARDY, Be ...

2003 Volume 51 Issue 1 Pages 36-41
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.36

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This paper summarizes a number of instrumental designs and configurations that have been developed by the Middle Atlantic Mass Spectrometry Laboratory for the miniaturization of time-of-flight mass spectrometers that will be used in environmental, bioagent detection, and diagnostics applications. All are “linear” designs, that is: ions are focused to a detector located within a line-of-sight of the ion source; no reflectrons are used. All are also “dynamic” instruments, using pulsed ion extraction and/or other time-dependent electric fields. These mass analyzers have flight paths of approximately 3 inches, with mass resolutions of up to one part in 1200 and mass ranges over 66 kdaltons. The use of non-homogeneous electric fields is also proposed to further improve that performance. Some examples are given for the analysis of peptides and bacterial spores.

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The Electrospray and Combustion at the Mesoscale

Sebastian KAISER, Dimitrios C. KYRITSIS, Peter DOBROWOLSKI, Marshall B ...

2003 Volume 51 Issue 1 Pages 42-49
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.42

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An application of the electrospray to mesoscale combustion is studied, with the ultimate goal of coupling the combustor with direct energy conversion modules for power production. The combustor design relies on fuel dispersion by multiplexed electrosprays coupled with a series of catalytic meshes acting as ground electrode and initiators of the fuel oxidation. The combustor has a volume on the order of few cm³ and operates on jet fuel (JP8), which is electrosprayed at a flow rate on the order of 10 g/h with equivalence ratios varying from 0.35-0.70. The behavior of the electrospray in high temperature environments is examined and the phenomenology of the electrospray in the combustion chamber is visualized using planar laser-induced fluorescence from a fluorescent tag doped into the fuel. Combustion efficiencies on the order of 97% can be achieved with uniform temperatures at the catalyst in the range of 900-1,300 K (within ±5%) when the electrospray is operated in an unsteady mode, accompanied by a “hissing” sound characteristic of the onset of corona discharge. Remarkably, no fouling, soot, or NO_x were detected in the exhaust gases, which resulted in clean and efficient combustion of even environmentally problematic liquid hydrocarbons.

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Whole Virus Mass Analysis by Electrospray Ionization

Stephen D. FUERSTENAU

2003 Volume 51 Issue 1 Pages 50-53
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.50

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This article recounts the development of techniques that lead to the first mass measurement of an intact virus. The results of that experiment, based on the method of charge detection mass spectrometry (CD-MS), are described in the context of other ESI-MS approaches to ultra-high mass ion analysis. The limits of current charge measurement technology are described and prospects for improved virus mass detection with a CMOS integrated circuit ion detector are discussed.

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Future Mass from Miniaturized Mass Spectrometry to Micro Mass Spectrometry

Takashi NOHMI, Tetsuya MIYAGISHI

2003 Volume 51 Issue 1 Pages 54-66
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.54

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The recent development of the silicon technology effects the stream of the miniaturized mass spectrometry and its system. Trend of oil less also accelerated at the same time. Old oil pump and oil diffusion pump turned to dry pump and turbo molecular pump for example. In the program of Mars exploration and other space program, mass spectrometry is one of the useful techniques to analyze the chemical components of environments. In this paper the recent development of mini size mass spectrometry, which is handy type, and micro mass spectrometry is reviewed. The improvement toward compact size mass has been taken place in the every part of mass spectrometry system from soft ionization system, mass spectrometer to pumping system. Also this improvement wipes out contamination from the overflowed sample and oil system. As the result when higher sensitivity with less sample system overcomes the detection limit of dog nose, new era for mass spectrometer will be created as one of sensors, intelligent nose.

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REGULAR PAPERS

Protein and Synthesized Peptide pI Marker Analysis by Capillary Isoelectric Focusing Separation/Mass Spectrometry Using Sonic Spray Ionization

Yukiko HIRABAYASHI, Atsumu HIRABAYASHI, Kiyohito SHIMURA

2003 Volume 51 Issue 1 Pages 67-71
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.67

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Protein and synthesized-peptide pI marker analysis by using capillary isoelectric focusing separation/mass spectrometry (CIEF/MS) with a sonic spray ionization (SSI) interface, which has a buffer reservoir between the ion source and the separation capillary, has been demonstrated. Various proteins have often been used as pI markers for CIEF; however, they were unstable, so their pI could be changed from their expected ones. Therefore synthetic peptide pI markers are useful because of their higher stability and purity. However, the m/z of peptide pI markers are in the same range with those of the ions of polymers with a wide range of molecular weights due to ampholytes used for CIEF. As a result, detecting the protonated molecules of the peptide pI markers was difficult. In our work, we have optimized the scanning m/z range of a three-dimensional quadrupole (3DQ) ion-trap mass spectrometer to analyze of peptide pI markers and proteins, respectively, and to scan intensities of two ranges at the same time. Specifically, we separated the scanning range from 300 to 500 and from 700 to 1900. Using this method, carbonic anhydrase II, myoglobin, cytochrome-c, and four peptide pI markers were analyzed simultaneously by using CIEF/MS with an SSI interface, and these proteins were observed with reasonable pI values within the limit of the separation-power of this system.

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Kinetic Energy Measurements of Fragment Ions with a Time-of-Flight Mass Spectrometer

Yasuhiro SAKAI, Michihito K. KAWADA, Naoya MIYAUCHI

2003 Volume 51 Issue 1 Pages 72-76
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.72

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A new apparatus for kinetic energy measurements of fragment ions has been developed. This apparatus is based on a time-of-flight (TOF) mass spectrometer with a pulsed electron gun. We can distinguish between thermal ions and energetic ions on a TOF spectrum obtained from this apparatus, using the time-lag defined by the time between the ionization and the application of the extracting pulse. During this time-lag, since energetic ions are dispersed from the ionization region, we can't detect the energetic ions except ones that move in the direction of the detector. On the other hand, since the thermal ions move little, all of thermal ions can be detected. The kinetic energy distributions of fragment ions were calculated by considering the collection efficiency of ions. The performance of our new technique is evaluated by the comparison between our experimental data of kinetic energy distributions of the protons dissociated from a methane molecule and those of the previous works.

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COMMENTARIES

Mass Spectrometry for Exoterrestrial Biology and Electrospray

Masamichi YAMASHITA

2003 Volume 51 Issue 1 Pages 77-78
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.77

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Exo-terrestrial biology hits the core questions of modern science, where we are from and how we will be. Once we understand the function and mechanism of living systems in detail, we recognize a missing link between pre-biotic chemical evolution and the original ancestor of life. Space exploration searching extraterrestrial life on other planetary bodies might contribute to answer whether the principle that governs terrestrial life is limited specifically to earth or could be generalized to the universal law. Mass spectrometry has been an effective tool in this research field. In order to survey extant lives and fossil record, highly bio-specific and sensitive method should be selected. We can expect spin off from space driven technology development for which many severe requirements are imposed, such as physical size, mass, power consumption, and maintenance. Electrospray might be one of candidate technologies for space exploration at its capability to analyze bioassociated chemical species at high sensitivity and its wide range of applicability.

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Use of Nano Liquid Chromatography/Nanoelectrospray Ionization/Ion Trap Mass Spectrometer for Proteome Quantitation and Identification

Takao KAWAKAMI, Hisae ANYOJI, Toshihide NISHIMURA

2003 Volume 51 Issue 1 Pages 79-82
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.79

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We describe the potential and applicability of ion trap mass spectrometer to high-throughput expression proteome analysis. In an ion trap, the masses of the peptide ions are analyzed, and/or a particular ion can be selected to undergo collisions resulting in its fragmentation by which sequence information can be directly obtained. Equipped with nanoflow capillary liquid chromatography directly interfaced with nanoelectrospray ionization, ion trap mass spectrometer has been one of the standard systems to identify and quantify large numbers of proteins in complex protein mixtures. The characteristics including the stability, reliability and capability of MSⁿ essentially lead the mass spectrometer to the center of proteome-wide analysis.

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A Two-Dimension Ion Trap Technique for Time of Flight Mass Spectrometry

Shida SHEN, Craig WHITEHOUSE

2003 Volume 51 Issue 1 Pages 83-84
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.83

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REVIEWS

The Plant Movement and Its Related Proteins

Nobuyuki KANZAWA, Takahide TSUCHIYA

2003 Volume 51 Issue 1 Pages 85-90
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.85

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The sensitive plant, Mimosa pudica L. closes the leaves and hangs the petiole down when stimulated by touch or heat treatment. This bending of the petiole is caused by rapid shrinking of the lower side of motor organs called the pulvinus. MRI technique indicates that the water in the main pulvinus transfers from the flexor to the extensor during the rapid bending. The actin cytoskeleton in the motor cells plays in important role in the petiole bending. The actin molecules in Mimosa pudica L. is heavily tyrosine-phosphorylated. The bending of Mimosa pudica L. is correlated with reduced actin phosphorylation in the pulvinus.

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Mass Spectrometric Characterization for the Venom of Arthropod

Hideo NAOKI, Li DAI, Terumi NAKAJIMA

2003 Volume 51 Issue 1 Pages 91-95
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.91

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The venom of scorpion and spider contain numerous neurotoxic compounds like proteins, peptides, and polyamine blocking to the glutamatergic neuromuscular transmission or acting on various types of ion channels. Such biological active compounds in the venom grand are used for offensive or defensive purposes to paralyze or prey on other insects. This diversity of compounds and actions provide a wealth of bioactive compounds that is a resource of neuroscience research and a source of novel pharmaceuticals. Among these studies mass spectrometry is used as one of the unique characterization method for such venom from the insect.

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Genes Encoding Snake Neurotoxins and Their Expression Products

Toru TAMIYA

2003 Volume 51 Issue 1 Pages 96-100
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.96

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The venom of the sea snake Laticauda semifasciata contains α-neurotoxins (erabutoxins) and phospolipases A₂. α-Neurotoxins bind specifically to the nicotinic acetylcholine receptor and block the binding of acetylcholine to the receptor at neuromuscular junctions. Phospholipases A₂ inhibit to release neurotransmitter, acetylcholine, at neuromuscular junctions. The genes encoding these neurotoxins evolve via accelerated evolution including gene duplication and form multi-gene family. Thus there are many kinds of genes encoding these neurotoxins. However, some of the gene expression products could not be identified by the traditional methods. According to the development of analytical methods like on-line LC-ES-MS, we can detect the minor protein components in the venom of L. semifasciata.

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Nanobio RNA Architecture

Tan INOUE

2003 Volume 51 Issue 1 Pages 101-107
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.101

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New methods for designing and constructing nanobio RNA molecules are described and discussed. One of the naturally occurring catalytic RNA called Group I intron has been considered as the highly sophisticated assemblage of physically separable structural units termed “modular units.” The intron's crystal structure and 3D models are well established. On the basis of these studies, artificial RNA and RNP molecules were designed by employing a computer program for 3D molecular modeling of nucleic acids and protein. And the small scale in vitro selection technique was also successfully performed for obtaining new modular RNA units with specific roles in the modified natural RNAs. The future application is highly expected in the field of nanobio RNA science and engineering.

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Rapid Discrimination of Pathogenic Bacteria by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Yasuyuki ISHIDA

2003 Volume 51 Issue 1 Pages 108-113
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.108

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Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has attracted a great deal of attention in the field of chemotaxonomy as a potential tool for rapid and convenient bacterial differentiation. It has been demonstrated that several bacteria including pathogens can be discriminated and/or identified at the genus, species, and even strain level based on fingerprinting the protein or lipid patterns of the resulting mass spectra. In this review, firstly, the instrumental and methodological aspects of MALDI-MS for bacterial analysis are briefly discussed. Then, some typical applications of MALDI-MS to the discriminative analysis of various pathogenic bacteria will be discussed in detail.

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Determination Methods for Vero Toxins Produced by Enterohemorrhagic Escherichia coli

Fumio KONDO, Masahiro SUZUKI

2003 Volume 51 Issue 1 Pages 114-118
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.114

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During the past 20 years, outbreaks of enterohemorrhagic Escherichia coli (EHEC) have been increasing worldwide and have been recognized as a potential health concern. Vero toxins produced by EHEC seem to be the most common cause of hemolytic uremic syndrome. Rapid diagnosis of EHEC infection is important to prevent the expansion of infection. Diagnosis is carried out by both isolation of EHEC and detection of Vero toxins in fecal extracts or fecal cultures. This review describes briefly about the current knowledge of the EHEC and Vero toxins, and about the determination methods for Vero toxins. The attempt to identify Vero toxins by electrospray ionization-liquid chromatography/mass spectrometry is also discussed.

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Volcanic Gas and Prevention of Disaster

Junichi HIRABAYASHI

2003 Volume 51 Issue 1 Pages 119-124
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.119

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A large amount of SO₂ gas was discharged from Miyakejima volcano since the end of September, 2000. The averaged SO₂ flux was about 50,000 ton/day in 2000. About 4,000 people could not returned to the island, because SO₂ gas has been discharged, and more than 5 ppm of SO₂ gas concentrations has been observed frequently around the island. In generally, volcanic gas contains mainly water vapor. The dry gas is largely composed of HF, HCl, SO₂ , H₂S and CO₂ with small amount of N₂, H₂, He, Ar, CH₄ and CO. HF, HCl, SO₂ and H₂S gases have high toxicity. The volcanic gas disaster occupied about 2.5% of volcanic disaster based on the dead since 1900. In Japan, disasters by volcanic gas occurred 28 times around eleven active volcanoes and 49 people were died during the recent 50 years. Occurrence of volcanic gas disaster is mainly dominated by the configuration of ground around fumarolic area and meterological conditions such as windless, cloudy, foggy weather and formation of inversion layer. SO₂ has been released at Oyama volcano in Miyakejima island for more than two years, and the inhabitants had to leave the island. Volcanic gas disaster is influenced by meteorological conditions and local geology. In case of big eruption, volcanic gas ascends to the stratospheric, and aerosol causes low temperature in the world. To reduce the disaster of volcanic gas, it is needed to monitor with a selective gas sensor and to alarm people the forecasted dangers.

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Current Situation on Destruction of Abandoned Chemical Weapons (ACWs) in China

Shuzo FUJIWARA

2003 Volume 51 Issue 1 Pages 125-128
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.125

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In China, there are more than 700,000 chemical weapons, which were ababndoned by the Japanese Imperial Forces after World War II. Todays, the work of destruction of ACWs in China has been carried on under the co-operation between the Japanese and the Chinese goverment in order to finish the disposal-work by the end of 2007. In this paper, introduced are the outline of current situation and issues on Destruction of ACWs in China.

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COMMENTARIES

The Present Condition of Military Arms Processing

Mine Action in Cambodia Destruction Project of Abandoned Chemical Weapon in China

Takashi NOHMI, Masahisa SHIGEMATSU

2003 Volume 51 Issue 1 Pages 129-145
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.129

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In 33rd meeting of division of Fundamentals, Ionization and Ion Chemistry in Mass Spectrometry held in Tokyo on Sept. 30th 2000, Dr. Shuzou Fujiwara from National Institute of Advanced Industrial Science and Technology, explained the destruction project of abandoned chemical weapon in China (DACW). Also, in 36th meeting on Nov. 2nd 2002 was held in Tokyo and the policy for NBC (Nuclear, Bio and Chemical weapon) was picked up as the main topics. In this meeting, the detection of explosives by Mass Spectrometry and the recent movement of DACW was discussed. In this paper, the recent movement on the mine action in Cambodia and DACW is explained. The trace analysis techniques of Mass Spectrometry might be useful to sniff the explosives. Further development in Mass Trace Analysis Technique is required in clearance task.

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Strategy against Infections of Virions and Bovine Spongiform Encephalopahty (BSE) Prion

Sei-ichi MANABE

2003 Volume 51 Issue 1 Pages 146-152
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.146

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The prion proteins and virions were introduced as typical causative agents of BSE and epidemic virus disease such as AIDS. The process validation on confirmation of removal and/or inactivation of these agents at the purification step in bio-drug manufacturing process was described briefly and this validation is the most effective strategy against the fear of the infections. The mass spectrometry about the infectious agents might give fruitful contribution to the development of the virus removal filter developed recently in order to complete the process varidation.

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REGULAR PAPERS

Effect of Human Activity and Contribution of Mass Spectrometry on Environment

Kunihiko TAKEDA, Yoshihiro MARUYAMA, Mitsuru TANAHASHI

2003 Volume 51 Issue 1 Pages 153-162
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.153

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The results of the conceptual study on the effects of human activity on the Earth's environment, classified into regional and global issues, are summarized. Pollution by various pollutants in air and water has been greatly improved since the 1970s in Japan, and the toxicity of dioxin has been found to be slight. The number of designated victims of pollution disease and the death rate of infants have been decreasing, and the average life span in Japan ranks among the top in the world. Based on these facts, regional environmental problems can be said to be insignificant. On a global scale, it was not possible to indicate the deterioration of the Earth's environment from the viewpoint of engineering because the reason behind global warming is unclear, the destruction of the ozone layer has been scientifically solved, and the exhaustion of natural resources cannot be certified through direct scientific evidence. These reasons suggest that the recognition that the environment is growing worse is possibly incorrect, and misguided efforts in the engineering field based on such assumptions will come to nothing. Rather, more attention should be paid to the diffusion of poisons in the environment in a recycling society, as it will possibly increase the load on the environment.

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Hydrogen Atmosphere Effect on Vaporization of Li₂TiO₃ by means of High Temperature Mass Spectrometry

Tsuyoshi HOSHINO, Masaru YASUMOTO, Yoichi TAKAHASHI, Takayuki TERAI, M ...

2003 Volume 51 Issue 1 Pages 163-167
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.163

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The atmosphere controlled high temperature mass spectrometer has provided the vapor pressure data for a promising tritium breeding material, Li₂TiO₃, under condition of low-pressure hydrogen atmosphere. The observed vaporization behavior of Li₂TiO₃ under hydrogen addition is presented here. It was pointed out that hydrogen addition may cause formation of non-stoichiometric composition phase. For elucidating its possible non-stoichiometric character, the composition of Li₂TiO₃ has been investigated mainly by means of thermogravimetry. The results revealed that Li₂TiO₃ has doubly non-stoichiometric composition, Li_2-xTiO_3-y

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Removal of Endocrine Disruptors by Selective Sorption Method using Activated Carbons

Boo Ok YOON, Shin KOYANAGI, Takao ASANO, Mariko HARA, Akon HIGUCHI

2003 Volume 51 Issue 1 Pages 168-173
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.168

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We undertook a fundamental investigation of the removal of endocrine disruptors from aqueous solution by a sorption method using activated carbons, and compared the removal ability of endocrine disruptors by activated carbons to that by polydimethylsiloxane (PDMS) membranes. The activated carbons exhibited high removal ability of 1,2-dibromo-3-chloropropane (DBCP), 100 fold increased adsorption over that with PDMS membranes from aqueous solution of DBCP. The removal ratio of the endocrine disruptors, e.g., 1,2-dibromo-3-chloropropane, dibenzo-p-dioxin, and hexachlorocyclohexane, increased linearly in an aqueous solution with increasing the logarithm of P_ow of the endocrine disruptors. Almost complete removal of the endocrine disruptors (i.e.,>85%) was observed above log P_ow=3.5 in 25 mL of an aqueous solution using 0.05 g activated carbon. One aim of the present study is to use preferential sorption of chemical contaminants onto activated carbons for removal of the chemical contaminants from aqueous solutions including drinking water, beverages, milk, and human milk. When the removal of endocrine disruptors contained in milk or human milk is targeted, water soluble vitamins in the milk, such as vitamin B₂, vitamin B₁₂, and niacin are expected to be co-currently adsorbed on the activated carbons. Therefore, the present sorption method using activated carbon was applied to the removal of endocrine disruptors, such as di-n-octylphthalate, from the mineral water and 89% of di-n-octylphthalate was removed.

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Determination of Geosmin and 2-Methylisoborneol in Water using Solid Phase Extraction and Headspace-GC/MS

Yoshitomo IKAI, Sachiyasu HONDA, Naoki YAMADA, Shouko ONUMA, Ban-ichi ...

2003 Volume 51 Issue 1 Pages 174-178
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.174

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A sensitive and reliable method for the analysis of geosmin and 2-methylisoborneol (2-MIB) in water sample was developed. In this study, geosmin and 2-MIB in the sample were enriched 40-fold using a technique of solid phase extraction and the resulting enriched solution was subjected to automated headspace-GC/MS system to determine them. The separation of the compounds was performed on a DB-1 capillary column and the detection was carried out by EIMS operated in either full-scan or selected ion monitoring (SIM) mode. In the SIM mode, the two compounds were determinable at the concentration of 0.1 ppt, and the recoveries and coefficients of variations were 104 and 6.1% for geosmin, and 115 and 7.5% for 2-MIB, respectively, at the addition level of 1 ppt. Although the detection limits in full-scan mode were 10-fold worse than those of SIM, it allows both determination and mass spectroscopic identification of the two compounds at the level of 1 ppt.

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Eco-friendly Lubricating Oil: Effects of Functional Groups in Methyl Oleate and Olive Oil on Lubrication

Yoshiyuki MOCHIDA, Kunio KUDOU, Hiroshi OOKOUCHI, Gorou ARAI, Shigeo N ...

2003 Volume 51 Issue 1 Pages 179-186
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.179

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The lubrication characteristics of the olive oils, which are used as biodegradable lubricants, on the steel ball were examined on the viewpoint of their growing area and quality of the olive oil. The discoloration of virgin olive oil and the friction face and/or the friction force of the steel ball were found to be dependent on their growing area as well as pure olive oil.
  Property of the constituent metal constituents of steel ball on the air oxidation of methyl ester of oleic acid, which is major constituent fatty acid of olive oil and the lubrication characteristics of the resulting oxidation products, were investigated. The autoxidation of methyl oleate under the existence of each acetylacetonatos of Cr, Mn, Fe, Ni, Cu, and V was carried out by blowing dry air at 80°C. All the metal salts except V facilitated the oxidation. The metals employed affect the yields and the types of the products, i.e., hydroperoxide, hydroxide and epoxide whom the functional group exists for the center location of molecular chain.
  Friction test for ball bearing was conducted by using each oxidation product and parent methyl oleate. The surface of the steel ball was the abrasive wear condition by hydroperoxide. The hydroxide gave excellent lubrication characteristics by hydroxy group adsorbed on the surface of steel ball. Epoxide increased the coefficient of friction. Methyl linoleate, having two double bonds, provided the flatted frictional surface at the ball bearing, but it is easy to be oxidized.
  To sum up the major characteristics of the autoxidation products which affect friction surface of steel ball, the function groups of center position in molecular chain of methyl oleate are of most significance. It was found that double bond and hydroxyl function of α-position of double bond are effective under the boundary lubrication.

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Significance of Odor Sensing and Roasted Smell of Wood

Maya MAEKAWA, Takashi NOHMI, Tatsuru INOUE, Akon HIGUCHI

2003 Volume 51 Issue 1 Pages 187-195
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.187

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Odor perception is the only one of our five senses and reaches beyond the time and space. In the ancient times odor was used more often in order to discriminate, foreknow and avoid the existing danger. However, the civilized life style has taken away the original sharpness of our five senses. We surveyed the nature and explained the usefulness of the active odor recognition like the river selection by odor in salmon case. Odor perception enables creatures to sense the outer world, for example, sniffing the future world of the emerging danger and the past world by tracking the trace of bait for their survival. We examined the burn smell of wood as an example of the present odor detection. The decomposition products of cellulose and perfume of the wood were generated when the wood was heated and pyrolized. In the case of wood, the detection temperature of the smell of burnt levoglucosan was observed from 200°C, a low temperature as compared with 300°C in the case of cellulose. When levoglucosan was diluted in the hot decomposition products of wood, the adsorbed amount of levoglucosan at the cold point in column decreased and levoglucosan was detected at a lower temperature.

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The Fragmentation of Amine Cluster Ion Including HCl
-Proton Affinities of Drugs of Abuse-

Shigeki MATSUMURA, Hideyuki TAKEZAWA, Kimio ISA

2003 Volume 51 Issue 1 Pages 196-200
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.196

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The fragmentation of the cluster ion, [A₁+HCl+A₂+H]⁺ of amine bases A₁ and A₂, is studied by the BEBE type tandem mass spectrometer. The cluster ion, [A₁+HCl+A₂+H]⁺, is generated by the fast atom bombardment (FAB) ionization of mixture of two hydrochlorides of amines. The precursor ion is selected by the first analyzer (BE) and the product ions are scanned by the second analyzer (B/E linked scanning). The fragmentation of [A₁+HCl+A₂+H]⁺ yields two protonated monomers, [A₁+H]⁺, [A₂+H]⁺, and protonated heterodimer, [A₁+HCl+A₂+H]⁺. The relative abundances of [A₁+H]⁺ and [A₂+H]⁺ from the fragmentation of [A₁+HCl+A₂+H]⁺ are found to be related to their relative proton affinities and are used to determine the proton affinities (PAs) of methamphetamine and its analogs. The PA of methamphetamine is estimated to be 965 kJ/mol.

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Application for Forensic Science of Combustion Gas Analysis using GC/MS

Masatoshi MORINAGA

2003 Volume 51 Issue 1 Pages 201-204
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.201

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When a burned cadaver is found at the fire scene, an analysis of carbon monoxide-hemoglobin in the blood of victim is carried out to test the level of carbon-monoxide intoxication. However, carbon monoxide-hemoglobin could not be conformed in the blood of victim who used kerosene or gasoline as an accelerant. In such cases, the vital signs of victim having been injured by fire before the deaths were scarcely observed. The author performed that using a gas chromatography/mass spectrometry (GC/MS) was effective for an analysis of the hydrocarbon compounds in blood.

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Relationship between the Detectable Amount of Oil Component in Tatami and the Combustion Condition at the Scene of Arson

Yoshio KOBAYASHI, Takashi NOHMI, Yoichi SHIMOIKE, Hiroshi UENO, Maya M ...

2003 Volume 51 Issue 1 Pages 205-215
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.205

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The purpose of this study is to estimate the amounts of kerosene poured at the scene of arson. Several analytical methods have been carried out to detect kerosene in fire debris. There is no study to compare the methods quantitatively. First we discussed comparison about several analytical methods, and got the conclusion that the most sensitive method was found to be the analysis using gas chromatography/mass spectrometry (GC/MS) after extracting by ether. The detection limit of this methed was 0.05 µg/g.
The kerosene concentration of tatami had an effect on the condition of combustion. We estimated the diffusion speed of kerosene sprinkled on tatami. We conducted experiments to check the condition of tatami burning, due to the amount of kerosene. Furthermore, we showed the evidence to get fire debris from the inside not the surface to get information about the kerosene amount.

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Atmospheric Influence on Elimination Behaviors of Carbon Substances in Hydrolysis Products of Aluminum Alkoxides

Takahisa TSUGOSHI, Takaaki NAGAOKA, Koji WATARI

2003 Volume 51 Issue 1 Pages 216-219
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.216

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In the previous report, it was disclosed using the evolved gas analysis-mass spectrometry that the non-reacted alkoxyl group existed in hydrolysis product of aluminum alkoxides. However the heating atmosphere was helium or vacuum. In this paper, the influence of heating atmosphere, i.e., partial pressure of oxygen, was investigated. As a result of heating in the atmosphere containing oxygen, the non-reacted alkoxyl group was oxidized to CO₂ and H₂O before the dehydration from the aluminum hydroxide.

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Analysis of Electro-Ceramics by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

Masahiro OISHI, Keiichi FUKUDA

2003 Volume 51 Issue 1 Pages 220-223
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.220

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Analysis of electro-ceramics devices requires quantitative analysis of major and minor elements with high sensitivity and a spatial resolution of 10 µm. A new semi-quantitative method was developed using Laser Ablation ICP-MS. Ferrite and ceramic samples were prepared to verify this method. Semi-quantitative values obtained by LA-ICP-MS were in good agreement with reference values obtained by X-ray fluorescence analysis (XRF).

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The Investigation of Fast-GC/MS Analysis with Volatile Organic Compounds

Shinji HUKUMOTO, Yoshihiro SAITO, Yoshiyuki OKAMURA, Takaharu KITSUWA

2003 Volume 51 Issue 1 Pages 224-228
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.224

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The volatile organic compounds (VOCs) exist in tap water and environment water. Measurement of VOCs is necessary by the regulations system. The experiments are carried out by Purge-Trap GC/MS or Head Space GC/MS. Now 23 compounds of VOCs are monitored in Japan by the present regulation. Generally about thirty minutes is required to run one sample. It is essential to shorten the time for analysis. In this paper we describe the effect of shortening the length of the column on the runtime of head space-GC/MS.

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Structural Study of Dried Linseed Film using Two-Stage Pyrolysis-Gas Chromatography/Mass Spectrometry

Noriyasu NIIMURA, Naoya KISHI, Tetsuo MIYAKOSHI

2003 Volume 51 Issue 1 Pages 229-234
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.229

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A dried linseed film was analyzed by two-stage pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to investigate its structure and pyrolysis mechanisms. Heating furnace temperatures appropriate to the pyrolysis were determined to be 300°C and 600°C by thermogravimetry/differential thermal analysis-mass spectrometry (TG/DTA-MS). The dried linseed film was then pyrolyzed at 300°C and 600°C. From the pyrolysis at 300°C, saturated and monoenyl fatty acids were detected, and the relative peak intensities of hexadecanoic acid and of octadecanoic acid were highest. These fatty acids are the pyrolysis products of the terminal groups. The dried linseed film is terminated with saturated and monoenyl fatty acid esters, especially with hexadecanoic acid ester and octadecanoic acid ester. From the pyrolysis at 600°C, alkenes, alkanes and fatty acids were detected. Some alkenes and alkanes have carbon chains longer than the side chains of the glycerides. The alkenes and alkanes are the pyrolysis products of the glyceride polymers generated by the autoxidative C-C cross-linking. The formation of fatty acids is also attributed to the cross-links of the glyceride polymers. These results reveal that autoxidative cross-linking proceeds through the polymerization of linseed oil.

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TG-MS Study on Thermal Decomposition of Polystyrene

Tadashi ARII

2003 Volume 51 Issue 1 Pages 235-241
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.235

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Thermal decomposition of polystyrene in helium atmosphere was successfully studied by TG-DTA coupled with evolved gas analysis using mass spectrometry (TG-MS and TG-GC/MS) and sample-controlled TG (SCTG). TG-DTA showed a single decomposition step at 350-500°C, while SCTG completed below 300°C. The pyrogram of TG-GC/MS for the evolved gases formed by rapid heating agreed approximately with that of a previous reported pyrolysis-GC, and monomer, dimer, and trimer were clearly observed as the main degradation products. In linear heating experiments formation behavior of trimer was different from that of monomer and dimer, and was observed at the higher temperature side with increasing heating rate. In SCTG the reaction model governing the thermal decomposition of polystyrene was easily attributed by the shape of experimental curve, and corresponding kinetic model was reaction of a random scission in the main chain with L=3, where L is the smallest polymerization degree of polymer that does not evaporate. Presumably, formation of trimer was attributed to the secondary reaction during the thermal process.

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Elimination Processes of Guest Molecules from the Inclusion Compounds of Deoxycholic Acid

Takayoshi KIMURA, Yuichi KASAI, Tomohide TSUJIMOTO, Emi KAWAMURA, Tada ...

2003 Volume 51 Issue 1 Pages 242-246
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.242

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Thermal behaviors of the inclusion compounds of deoxycholic acid with methanol, ethanol, propane-1-ol, propane-2-ol, and butane-1-ol have been studied by TG-DTA-MS and DSC. Liberation processes of guest molecules from their inclusion compounds of methanol, ethanol were carried out in a single step. Those of propanols and butane-1-ol from the corresponding inclusion compounds proceed in complicated steps. The elimination temperatures, enthalpies and the activation enthalpies of eliminations have been determined by TG, DSC, and MS.

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Collisionally Activated Dissociation Mass Spectrometric Analysis of Alkali Halide Triple Ion Adduct Monosaccharide Ions

Nora MARTINEZ, Kimio ISA, Minoru HATANAKA, Ryuji NAKATA

2003 Volume 51 Issue 1 Pages 247-255
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.247

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Adduct ions of monosaccharide molecules with alkali halide triple ions were analyzed by Fast Atom Bombardment (FAB) and Collisionally Activated Dissociation (CAD) techniques. The adduct ions generally appeared in the form of [S+AiXAj]⁺, where S=monosaccharide molecule, Ai⁺=Na⁺, Aj⁺=Cs⁺, and X^-=Cl^-, respectively. First, in FABMS spectra, (AiXAj)⁺ adduct monosaccharide molecule ions were identified; second, from the mass spectra, the precursor ions were selected, and it was possible to verify their product ions in the CAD spectra. Then, the relative intensities of the product ions were compared. In the present paper, we report the fragmentation processes of [S+AiXAj]⁺, the main (AiXAj)⁺, Ai⁺, Aj⁺, (S+Ai)⁺, (S+Aj)⁺ product ions, the relative intensities of these product ions, and try to explain the interactions occurring in [S+AiXAj]⁺ adduct ions.

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TECHNICAL REPORT

Development of a Novel Bacterial Biodegradation Test Method of Non-ionic Surfactants using ¹⁸O-Labelled Water

Atsushi SHIBATA, Hiroaki SATO, Hiromichi YOSHIKAWA, Hiroto TAMURA

2003 Volume 51 Issue 1 Pages 256-259
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.256

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In order to investigate the oxidative biodegradation mechanisms of octylphenol polyethoxylate (OPEO) by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS), fundamental conditions for the bacterial biodegradation test method using ¹⁸O-labelled water as an incubation medium were examined. Since ¹⁸O-labelled water is a valuable reagent, reduction of incubation medium down to 200 µL could be achieved. Furthermore, to recover OPEO degradation intermediates from a minimum amount of the medium containing basal salt, a simple solid-liquid extraction procedure was introduced. The combination of the biodegradation test using ¹⁸O-labelled water and MALDI-MS measurement thus could provide a conclusive biodegradation mechanism by the observation of incorporation of ¹⁸O atoms into the carboxyl group of OPEC during the biodegradation process.

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NEW FACE

Sequencing Novel Peptides from Solitary Wasps by Nested CID/PSD

Miki HISADA

2003 Volume 51 Issue 1 Pages 310-316
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.310

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We examined the applicability of the “nested” collision induced dissociation/post-source decay (CID/PSD) method to sequencing of novel peptides from solitary wasps which have neurotoxic venom for paralyzing other insects. The CID/PSD spectrum of a ladder peptide derived from an exopeptidase digest was compared with that of the intact peptide. The mass peaks observed only in the CID/PSD spectrum of a ladder peptide were extracted as C-terminal fragment ions. Assignment of C-terminal fragment ions enabled calculation of N-terminal fragment masses, leading to differentiation between N-terminal fragment ions and internal fragment ions. Furthermore, a method incorporating nested CID/PSD combined with endopeptidase digestion is described as an approach to determine the sequence of N-terminally modified peptides. The information from immonium and related ions observed in the CID/PSD spectrum was used for the selection of a suitable endopeptidase for the digestion of peptides. These nested CID/PSD methods allowed rapid and sensitive identification by removing ambiguity in the assignment of the fragment ions, and proved useful for sequencing unknown peptides, in particular those available as natural products with a limited supply.

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Development and Applications of Tandem Pyrolyzer-GC-MS System

Tetsuo HIGUCHI

2003 Volume 51 Issue 1 Pages 317-318
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.317

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A Tandem Pyrolyzer which has two micro-furnaces in vertical position was developed. The temperature of two furnaces can be set up arbitrarily. Moreover, reagent gas such as air, oxygen, and others can be introduced into the 2nd micro-furnace to carry out chemical reaction between pyrolyzates of sample which thermally decomposed in the 1st micro-furnace and reagent gas. In this study, high sensitivity GC-MS was used as a detector for the tandem pyrolyzer. In case of study by using air as a reagent gas at the 2nd furnace, large amount of oxygen will flow into the MS ion source and may damage the filament. To avoid the problem, material and form of filament were examined. Chemical hazardous materials in the pyrolyzate of poly(vinyl chloride) were identified using a tandem pyrolyzer combined with a capillary GC-MS. On this study, poly(vinyl chloride) was pyrolyzed in the 1st furnace maintained at 600°C in helium, and then pyrolyztes were introduced again into the 2nd furnace in order to obtain the further information in air circumstances. As a result, aromatic compounds, acids, and aldehydes, in addition to a trace level of chlorinated aromatics such as pentachlorophenol which was one of precursor compounds of dioxin, also dioxins and PCBs were detected. The tandem pyrolyzer-GC-MS system is very powerful analytical tool to characterize the pyrolyzate of polymers in different circumstances.

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Evaluation of Biodegradability of Polymeric Materials by Analytical Pyrolysis and Mass Spectrometry

Hiroaki SATO

2003 Volume 51 Issue 1 Pages 319-323
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.319

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In order to develop a noble evaluation method for biodegradability of polymeric materials, various biodegradable polymers have been characterized mainly by using pyrolysis-gas chromatography (Py-GC) and matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS). First, the degree of biodegradation of poly(butylene succinate-co-butylene adipate) (PBSA) film samples during the soil burial degradation test was evaluated by Py-GC. This technique was further applied to evaluate the compositional change of biodegradable polymer blends during enzymatic degradation test. On the other hand, enzymatic degradation behavior of a biodegradable polyester with a controlled terminal structure was monitored by MALDI-MS mainly focused on the changes in molecular weight distribution and terminal structure. Finally, biodegradation intermediates of nonionic surfactant were characterized by MALDI-MS. By using ¹⁸O-labelled water as an incubation medium, detailed biodegradation mechanisms of the surfactant were proposed.

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Study of Phosphoprotein and Phosphopeptide by Mass Spectrometry

Tomoya KINUMI

2003 Volume 51 Issue 1 Pages 324-329
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.324

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Protein phosphorylation at serine, threonine and/or tyrosine residue plays a crucial role in cell signaling. Many different classes of protein kinases that are responsible for this reaction have been characterized. A conventional protocol utilizes [³²P-γ] ATP as a radioactive donor and evaluates the radioactivity incorporated into the substrate. I am interested in the structural analysis of phosphopeptides and in an assay system for protein phosphorylation using mass spectrometry which allow a quick and accurate analysis without using radioisotopes. Several methodologies have been developed to determine the phosphorylation sites and kinase activity by using mass spectrometry. In this paper, I present three applications for phosphoprotein and phosphopeptide analysis using mass spectrometry as follows, 1) the determination of in vivo phosphorylation site using a streamed line combination of two-dimensional gel electrophoresis and LC-MS/MS, 2) the structure analysis of long chain phosphopeptide by in-source decay using MALDI-TOF/MS, 3) kinase assay using biotinylated peptide substrate by MALDI-TOF/MS.

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Evaluation of Chiral Recognition of Oligosaccharides using FABMS

Motohiro SHIZUMA

2003 Volume 51 Issue 1 Pages 330-333
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.330

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Chiral recognition ability of permethylated oligosaccharides toward amino acid derivatives was evaluated by the FAB mass spectrometry/enantiomer labelled guest method. Among the permethylated oligosaccharides, fructofuranose (MeFruNys) showed remarkable chiral recognition ability. It was clarified that MeFruNys adopts “induced-fitting chiral recognition” as the chiral recognition mechanism. Moreover, new linear chiral hosts were designed on the basis of the structural features of MeFruNys, and then, synthesized. Their host also showed chiral recognition. One of the hosts was utilized as a reagent for evaluation of optical purity of the chiral guests.

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Studies on Unimolecular Metastable Decomposition of Several Organic Compounds

Yutaka TAKAHASHI

2003 Volume 51 Issue 1 Pages 334-336
Published: 2003
Released on J-STAGE: October 16, 2007

DOIhttps://doi.org/10.5702/massspec.51.334

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The unimolecular metastable decomposition mechanism of several organic compounds, which have small molecular weights, was investigated in this study by means of mass-analyzed ion kinetic energy (MIKE) spectrometry, D-labeling technique and molecular orbital (MO) calculations. Accurate mass determination is also described by using a multiple sprayers Nano-ESI arrangement on a double-focusing magnetic sector instrument in this thesis. For example, ‘Unimolecuar HCl Loss from the Molecular Ions of Chlorophenols, a “Ring-walk” Mechanism for a Chlorine Atom’ is described in this abstract. The loss of hydrogen chloride (HCl) is one of the main fragmentation processes in the molecular of o, m-, and p-chlorophenols in the metastable time window. By investigation of D-labeled compounds, it could be established that the eliminated HCl molecule contains only the hydroxyl hydrogen atom, not other benzene ring hydrogen atoms. This process is rationalized by the so-called “ring-walk” mechanism for a chlorine atom.

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