Rapid detection of drugs in biofluids using atmospheric pressure chemi/chemical ionization mass spectrometry

We have demonstrated that, with simple pH adjustment, volatile drugs such as methamphetamine, amphetamine, 3,4‐methylenedioxymethamphetamine (MDMA), ketamine, and valproic acid could be analyzed rapidly from raw biofluid samples (e.g. urine and serum) without dilution, or extraction, using atmospheric pressure ionization. The ion source was a variant type of atmospheric pressure chemical ionization (APCI) that used a dielectric barrier discharge (DBD) to generate the metastable helium gas and reagent ions. The sample solution was loaded in a disposable glass pipette, and the volatile compounds were purged by nitrogen gas to be reacted with the metastable helium gas. The electrodes of the DBD were arranged in such a way that the generated glow discharge was confined within the discharge tube and was not exposed to the analytes. A needle held at 100–500 V was placed between the ion‐sampling orifice and the discharge tube to guide the analyte ions into the mass spectrometer. After pH adjustment of the biofluid sample, the amphiphilic drugs were in the form of a water‐insoluble oil, which could be concentrated on the liquid surface. By gentle heating of the sample to increase the evaporation rate, rapid and sensitive detection of these drugs in raw urine and serum samples could be achieved in less than 2 min for each sample. Copyright © 2009 John Wiley & Sons, Ltd.     

Development and application of an internet electron microscopy system for the outreach program in Japan.

The development of a remotely operated scanning electron microscopy (SEM) system and its use by high school students and the public as an outreach program are reported. The SEM and the server are located in the National Institute for Materials Science, Tsukuba, Japan, with client computers installed at a science museum and high schools. Using a secure virtual private network system and scheduling/management groupware, observation of SEM images and energy dispersive X-ray analysis are widely and frequently performed throughout Japan.     

Forbidden Triples Containing a Complete Graph and a Complete Bipartite Graph of Small Order

For a graph G and a set \({\mathcal{F}}\) of connected graphs, G is said be \({\mathcal{F}}\) -free if G does not contain any member of \({\mathcal{F}}\) as an induced subgraph. We let \({\mathcal{G} _{3}(\mathcal{F})}\) denote the set of all 3-connected \({\mathcal{F}}\) -free graphs. This paper is concerned with sets \({\mathcal{F}}\) of connected graphs such that \({\mathcal{F}}\) contains no star, \({|\mathcal{F}|=3}\) and \({\mathcal{G}_{3}(\mathcal{F})}\) is finite. Among other results, we show that for a connected graph T( ≠ K ₁) which is not a star, \({\mathcal{G}_{3}(\{K_{4},K_{2,2},T\})}\) is finite if and only if T is a path of order at most 6.     

Distance-restricted matching extendability of fullerene graphs

A fullerene graph is a 3-connected cubic plane graph whose all faces are bounded by 5- or 6-cycles. In this paper, we show that a matching M of a fullerene graph can be extended to a perfect matching if the following hold: (i) three faces around each vertex in \(\{x,y:xy\in M\}\) are bounded by 6-cycles and (ii) the edges in M lie at distance at least 13 pairwise.     

Characterization of coal fly-ash particles by laser microprobe mass spectrometry

Laser microprobe mass spectrometry (LMMS) was applied to coal fly-ash particles prefractionated to homogeneous composition with respect to particle size and density. For major elements, semiquantitative results (<50% relative standard deviation) were obtained; and the characteristic density dependence found for Si, K, Ca and Fe was in good agreement with that obtained by scanning electron microscopy/energy-dispersive x-ray analysis (EDX). The relative sensitivity coefficients, based on concentrations evaluated from the EDX data, coincided with those obtained for the NBS glass particle standard in previous work.     

Ion/molecule reactions in the orifice-skimmer region of an atmospheric pressure Penning ionization mass spectrometer

Atmospheric pressure Penning ionization mass spectra of methanol were measured as functions of Ar or He gas pressure in the first vacuum chamber, the position of the skimmer, and the voltage applied between the orifice and the skimmer. When the orifice and the skimmer were coaxial with a distance of 4 mm, the distribution of CH3OH2+(CH3OH)n clusters was only weakly dependent on both Ar pressure (in the range of 19-220 Pa) and orifice-skimmer voltage (in the range of 1-45 V). The ion/molecule reaction CH3OH2+ + CH3OH --> CH3+(CH3OH) + H2O was observed in the free jet expansion, especially at high orifice-skimmer voltage values. When the orifice and the skimmer were off-centered and the distance between them was increased to 18 mm, the formation of large CH3OH2+(CH3OH)n clusters, as well as their dissociation, were seen. The endothermic proton transfer reaction, CH3+(CH3OH) + CH3OH --> CH3OH2+ + CH3OCH3, occurred at high orifice-skimmer voltage. The collision-induced dissociation of cluster ions by He gas in the first vacuum chamber was much more efficient than by Ar. These results demonstrated that the mass spectra are highly dependent on skimmer position and on orifice-skimmer voltage and that ions observed by mass spectrometry do not necessarily reflect the abundance of ions produced in the atmospheric pressure ion source.     

Young's double-slit interference observation of hot electrons in semiconductors

We have carried out Young's double-slit experiment for the hot-electron wave in man-made semiconductor structures with a 25-nm-space double slit in an InP layer buried within GaInAs, a 190-nm-thick GaInAsP hot-electron wave propagation layer, and a collector array of 80 nm pitch. At 4.2 K, dependences of the collector current on the magnetic field were measured and found to agree clearly with the double-slit interference theory. The present results show evidence for the wave front spread of hot electrons using the three-dimensional state in materials, for the first time, and the possibility of using top-down fabrication techniques to achieve quantum wave front control in materials.     

Microwave spectrum of the HD2O+ ion: inversion-rotation transitions and inversion splitting

Inversion-rotation spectral lines of the dideuterated hydronium ion, HD2O+, have been observed by a source-modulation millimeter- to submillimeter-wave spectrometer. The ion was generated by a hollow-cathode discharge in a gas mixture of D2O and H2O in a free-space cell. Ten inversion-rotation lines were measured precisely for the lowest pair of inversion doublets in the frequency region from 380 to 730 GHz. The observed lines include the most astronomically important transitions, 0(00) (-)-1(10)+ for the para species at 380 538.031(32) MHz and 1(01) (-)-1(11)+ for the ortho species at 728 420.189(34) MHz, which could be used as a radio astronomical probe investigating interstellar chemistry of deuterium fractionation. An analysis of the measured lines has yielded the rotational constants in the ground doublet states and the inversion splitting. The inversion splitting in the ground state was determined to be 808 866(34) MHz, that is, 26.980 87(113) cm(-1), where the numbers in parentheses give uncertainties estimated from the Jacobian matrix of the assumed centrifugal distortion constants. The determined inversion splitting is off by -0.51 cm(-1) from the predicted value of 27.49 cm(-1) by Rajamaki et al. using high-order coupled cluster ab initio calculation [J. Chem. Phys. 118, 10929 (2003)], and by -0.0510 cm(-1) from the observed value of 27.0318(72) cm(-1) by Dong et al. using high-resolution jet-cooled infrared spectroscopy [J. Chem. Phys. 122, 224301 (2005)] beyond the quoted uncertainty.     

Characterization of orphan monooxygenases by rapid substrate screening using FT-ICR mass spectrometry

Characterization of orphan enzymes, for which the catalytic functions and actual substrates are still not elucidated, is a significant challenge in the postgenomic era. Here, we describe a general strategy for exploring the catalytic potentials of orphan monooxygenases based on direct infusion analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR/MS). Eight cytochromes P450 from Bacillus subtilis were recombinantly expressed in Escherichia coli and subjected to a reconstitution system containing appropriate electron transfer components and many potential substrates. The reaction mixtures were directly analyzed using FT-ICR/MS, and substrates of the putative enzymes were readily identified from the mass spectral data. This allowed identification of previously unreported CYP109B1 substrates and the functional assignment of two putative cytochromes P450, CYP107J1 and CYP134A1. The FT-ICR/MS-based approach can be easily applied to large-scale screening with the aid of the extremely high mass resolution and accuracy.