Satoshi Ninomiya

Solid probe assisted nanoelectrospray ionization mass spectrometry for biological tissue diagnostics

To perform remote and direct sampling for mass spectrometry, solid probe assisted nanoelectrospray ionization (SPA-nanoESI) has been newly developed. After capturing the sample on the tip of the needle by sticking it to the biological tissue, the needle was inserted into the solvent-preloaded nanoESI capillary from the backside. NanoESI gave abundant ion signals for human kidney tissues and the liver of a living mouse. The method is easy to operate and versatile because any biological specimen could be sampled away from the mass spectrometer. Minimal invasiveness is another merit of this method.

Vacuum electrospray of volatile liquids assisted by infrared laser irradiation

RATIONALEnCurrent large cluster sources such as C(60) or argon utilize gas-phase sources which are of low-brightness and cannot be focused efficiently to better than 1 micron diameter spot size. The development of a high-brightness large cluster ion source is of critical importance to achieve high resolution in secondary ion mass spectrometry (SIMS) imaging of organics.nnnMETHODSnWe propose a new high-brightness large cluster ion source, and a technique for producing a stable electrospray of volatile liquids under vacuum. It is known that vacuum electrospray of volatile liquids such as water is extremely difficult because of freezing of the liquids introduced in vacuum by evaporative cooling. To avoid freezing, the tip of the electrospray emitter was irradiated by a continuous wave infrared laser.nnnRESULTSnWithout continuous laser irradiation the vacuum electrospray of a water/methanol solution was unstable with respect to the shapes of the Taylor cone and current, whereas continuous laser irradiation produced a stable electrospray of water. The typical modes of electrospray were clearly observed with an optical microscope even under vacuum conditions. A stable vacuum electrospray could be achieved by improving the vacuum pressure to suppress electric discharge and by using the laser to maintain the liquid state.nnnCONCLUSIONSnThis is the first description of the production of a stable vacuum electrospray of volatile liquids such as water. This vacuum electrospray technique can be expected to produce a novel high-brightness large cluster ion beam source.

Flash Desorption/Mass Spectrometry for the Analysis of Less- and Nonvolatile Samples Using a Linearly Driven Heated Metal Filament

AbstractIn this paper, the important issue of the desorption of less- and nonvolatile compounds with minimal sample decomposition in ambient mass spectrometry is approached using ambient flash desorption mass spectrometry. The preheated stainless steel filament was driven down and up along the vertical axis in 0.3xa0s. At the lowest position, it touched the surface of the sample with an invasion depth of 0.1xa0mm in 50xa0ms (flash heating) and was removed from the surface (fast cooling). The heating rate corresponds to ~104xa0°C/s at the filament temperature of 500xa0°C. The desorbed gaseous molecules were ionized by using a dielectric barrier discharge ion source, and the produced ions were detected by a time-of-flight (TOF) mass spectrometer. Less-volatile samples, such as pharmaceutical tablets, narcotics, explosives, and C60 gave molecular and protonated molecule ions as major ions with thermal decomposition minimally suppressed. For synthetic polymers (PMMA, PLA, and PS), the mass spectra reflected their backbone structures because of the suppression of the sequential thermal decompositions of the primary products. The present technique appears to be suitable for high-throughput qualitative analyses of many types of solid samples in the range from a few ng to 10xa0μg with minimal sample consumption. Some contribution from tribodesorption in addition to thermal desorption was suggested for the desorption processes.n Figureᅟ

Trace Level Detection of Explosives in Solution Using Leidenfrost Phenomenon Assisted Thermal Desorption Ambient Mass Spectrometry

The present paper demonstrates the detection of explosives in solution using thermal desorption technique at a temperature higher than Leidenfrost temperature of the solvent in combination with low temperature plasma (LTP) ionization. Leidenfrost temperature of a solvent is the temperature above which the solvent droplet starts levitation instead of splashing when placed on a hot metallic surface. During this desorption process, slow and gentle solvent evaporation takes place, which leads to the pre-concentration of less-volatile explosive molecules in the droplet and the explosive molecules are released at the last moment of droplet evaporation. The limits of detection for explosives studied by using this thermal desorption LTP ionization method varied in a range of 1 to 10 parts per billion (ppb) using a droplet volume of 20u2009μL (absolute sample amount 90-630u2009fmol). As LTP ionization method was applied and ion-molecule reactions took place in ambient atmosphere, various ion-molecule adduct species like [M+NO2](-), [M+NO3](-), [M+HCO3](-), [M+HCO4](-) were generated together with [M-H](-) peak. Each peak was unambiguously identified using Exactive Orbitrap mass spectrometer in negative ionization mode within 3u2009ppm deviation compared to its exact mass. This newly developed technique was successfully applied to detect four explosives contained in the pond water and soil sample with minor sample pre-treatment and the explosives were detected with ppb levels. The present method is simple, rapid and can detect trace levels of explosives with high specificity from solutions.

Development of sheath-flow probe electrospray ionization (SF-PESI)

Probe electrospray ionization (PESI) uses a sharp solid needle as electrospray emitter. This method was found to be applicable to the analysis of real-world samples with high concentrations of salts and detergents without sample pretreatment. Since PESI is only applicable to wet samples but not to dry samples, sheath-flow PESI (SF-PESI) has been developed. The metal needle was inserted into the fine plastic capillary with a protrusion of 0.1-0.2u2009mm from the capillary terminus. The solvent was supplied continuously through the capillary. At the lowest position of the probe, solvent flowing out from the capillary makes the sample wet and extracts the analytes from the surface. The extracted analytes were electrosprayed at the highest position of the needle. SF-PESI was successfully applied to samples such as narcotics, tablets, bill, fruits, potatoes, etc.

Probe electrospray ionization (PESI) mass spectrometry with discontinuous atmospheric pressure interface (DAPI).

Probe electrospray ionization (PESI) using a 0.2 mm outside diameter titanium wire was performed and the generated ions were introduced into the mass spectrometer via a discontinuous atmospheric pressure interface using a pinch valve. Time-lapse PESI mass spectra were acquired by gradually increasing delay time for the pinch valve opening with respect to the start of each electrospray event when a high voltage was applied. The opening time of the pinch valve was 20 ms. Time-resolved PESI mass spectra showed marked differences for 10 mM NaCl, 10−5 M gramicidin S and insulin in H2O/CH3OH/CH3COOH (65/35/1) with and without the addition of 10 mM CH3COONH4. This was ascribed to the pH change of the liquid attached to the needle caused by electrochemical reactions taking place at the interface between the metal probe and the solution. NaCl cluster ions appeared only after the depletion of analytes. For the mixed solution of 10−5 M cytochrome c, insulin, and gramicidin S in H2O/CH3OH/CH3COOH (65/35/1), a sequential appearance of analyte ions in the order of cytochrome c → insulin → gramicidin S was observed. The present technique was applied to three narcotic samples, methamphetamine, morphine, and codeine. Limits of detection for these compounds were 10 ppb in H2O/CH3OH (1/1) for the single sampling with a pinch valve opening time of 200 ms.

Alternating current corona discharge/atmospheric pressure chemical ionization for mass spectrometry

RATIONALEnAlthough alternating current (ac) corona discharge has been widely used in the fields of material science and technology, no reports have been published on its application to an atmospheric pressure chemical ionization (APCI) ion source. In this work, ac corona discharge for an APCI ion source has been examined for the first time.nnnMETHODSnThe ambient atmospheric pressure ac corona discharge (15u2009kHz, 2.6 kVptp ) was generated by using a stainless steel acupuncture needle. The generated ions were measured using an ion trap mass spectrometer. A comparative study on ac and direct current (dc) corona APCI ion sources was carried out using triacetone triperoxide and trinitrotoluene as test samples.nnnRESULTSnThe ac corona discharge gave ion signals as strong as dc corona discharge for both positive and negative ion modes. In addition, softer ionization was obtained with ac corona discharge than with dc corona discharge. The erosion of the needle tip induced by ac corona was less than that obtained with positive mode dc corona.nnnCONCLUSIONSnA good yardstick for assessing ac corona is that it can be used for both positive and negative ion modes without changing the polarity of the high-voltage power supply. Thus, ac corona can be an alternative to conventional dc corona for APCI ion sources.

Super‐atmospheric pressure ionization mass spectrometry and its application to ultrafast online protein digestion analysis

Pressure is a key parameter for an ionization source. In this Special Feature article, Lee Chuin Chen and colleagues review super-atmospheric pressure ionization MS with electrospray, corona-discharge-based chemical ionization, and field desorption. They routinely run their mass spectrometer with ion source pressures ranging from several to several tens of atmospheres. A number of strategies have been used to preserve the high vacuum of the instrument while working with a high-pressure (HP) ion source. A recent prototype uses a booster pump with variable pumping speed added to the first pumping stage of the mass spectrometer to regulate a constant vacuum pressure. Further, a new HP-ESI source allowing rapid (a few seconds) online protein digestion MS is also reported. Dr. Lee Chuin Chen is Associate Professor in the Department of Interdisciplinary Research at the University of Yamanashi (Yamanashi, Japan). His main research interest is the development of novel mass spectrometric methods for in-situ medical diagnosis.

Desorption Mass Spectrometry for Nonvolatile Compounds Using an Ultrasonic Cutter

AbstractIn this work, desorption of nonvolatile analytes induced by friction was studied. The nonvolatile compounds deposited on the perfluoroalkoxy substrate were gently touched by an ultrasonic cutter oscillating with a frequency of 40xa0kHz. The desorbed molecules were ionized by a dielectric barrier discharge (DBD) ion source. Efficient desorption of samples such as drugs, pharmaceuticals, amino acids, and explosives was observed. The limits of detection for these compounds were about 1xa0ng. Many compounds were detected in their protonated forms without undergoing significant fragmentation. When the DBD was off, no ions for the neutral samples could be detected, meaning that only desorption along with little ionization took place by the present technique.n Figureᅟ

Secondary ion yields for vacuum-type electrospray droplet beams measured with a triple focus time-of-flight analyzer.

RATIONALEnWe previously developed a massive cluster ion beam gun for secondary ion mass spectrometry (SIMS) in which the primary beam source is a vacuum electrospray. The secondary ion yields produced by this method had not yet been measured with a commercial time-of-flight (TOF) secondary ion mass spectrometer, and the ionization performance was unknown.nnnMETHODSnA vacuum-type electrospray droplet ion gun was connected to a triple-focus TOF analyzer. The flight time of the secondary ions was measured using a sample-bias pulsing method, because a short pulse of the electrospray droplet beam could not be obtained. The secondary ion yields of an amino acid sample produced by the electrospray droplet beams and atomic Ga ion beams were compared.nnnRESULTSnTOF secondary ion spectra were measured for the amino acid and peptide samples with a mass resolution of ~500 using the sample-bias pulsing method. The secondary ion yield of the amino acid sample produced with the 10 kV vacuum-type electrospray droplet beams was much higher than that produced by 10 kV Ga ion beams. In addition, the secondary ion yields for the peptide sample and amino acid samples were almost similar.nnnCONCLUSIONSnThis is the first report on secondary ion yields produced with vacuum-type electrospray droplet ion beams and measured with a semi-commercial TOF analyzer. The enhancement of secondary ion yields, in particular for relatively high-mass molecules, would be very useful in the SIMS analysis of a wide variety of biological samples. Copyright