Depth profiling in secondary ion mass spectrometry for ultra‐thin layer with nanometer order thickness by mesa‐structure fabrication

We attempted to make an accurate depth profiling in secondary ion mass spectrometry (SIMS) including backside SIMS for ultra‐thin nanometer order layer. The depth profiles for HfO₂ layers that were 3 and 5 nm thick in a‐Si/HfO₂/Si were measured using quadrupole and magnetic sector type SIMS instruments. The depth profiling for an ultra‐thin layer with a high depth resolution strongly depends on how the crater‐edge and knock‐on effects can be properly reduced. Therefore, it is important to control the analyzing conditions, such as the primary ion energy, the beam focusing size, the incidence angle, the rastered area, and detected area to reduce these effects. The crater‐edge effect was significantly reduced by fabricating the sample into a mesa‐shaped structure using a photolithography technique. The knock‐on effect will be serious when the depth of the layer of interest from the surface is located within the depth of the ion mixing region due to the penetration of the primary ions. Finally, we were able to separately assign the origin of the distortion to the crater‐edge effect and knock‐on effect. Copyright © 2012 John Wiley & Sons, Ltd.     

Simultaneous determination of dl-lactic acid and dl-3-hydroxybutyric acid enantiomers in saliva of diabetes mellitus patients by high-throughput LC–ESI-MS/MS

A simultaneous determination method for the enantiomers of chiral carboxylic acids by the combination of ultraperformance liquid chromatography and mass spectrometry (UPLC-MS/MS) has been developed. (S)(+)-1-(2-Pyrrolidinylmethyl)-pyrrolidine (S-PMP) was used as the derivatization reagent for the high-throughput determination of biological chiral carboxylic acids, i.e., lactic acid (LA) and 3-hydroxybutyric acid (HA). The S-PMP efficiently reacted with the carboxylic acids under mild conditions at room temperature in the presence of 2,2'-dipyridyl disulfide and triphenylphosphine. The resulting S-PMP derivatives were highly responsive in the electrospray ionization (ESI)-MS operating in the positive-ion mode and gave characteristic product ions during the MS/MS, which enabled the sensitive detection using selected reaction monitoring. The derivatization was effective for the enantiomeric separation of the chiral carboxylic acids, and the resolution values of DL-LA and DL-HA were 4.91 and 9.37, respectively. Furthermore, a rapid separation of the derivatives of DL-LA and DL-HA within 7?min was performed using the UPLC system. The limits of detection on the column were in the low femtogram range (5-12?fg). The proposed procedure was successfully applied for the determination of the D- and L-isomers of LA and HA in the saliva of diabetes mellitus (DM) patients and healthy volunteers. The D-LA in DM patients was clearly higher than that in normal subjects. The derivatization followed by UPLC-ESI-MS/MS enabled the enantiomeric separation and detection of trace amounts of LA and HA in human saliva with a simple pretreatment and small sample volume.     

Stabilization of atmospheric carbon dioxide via zero emissions-An alternative way to a stable global environment. Part 2: A practical zero-emissions scenario

Following Part 1, a comparison of CO2-emissions pathways between "zero-emissions stabilization (Z-stabilization)" and traditional stabilization is made under more realistic conditions that take into account the radiative forcings of other greenhouse gases and aerosols with the constraint that the temperature rise must not exceed 2 °C above the preindustrial level. It is shown that the findings in Part 1 on the merits of Z-stabilization hold under the more realistic conditions. The results clarify the scientific basis of the policy claim of 50% reduction of the world CO2 emissions by 2050. Since the highest greenhouse gas (GHG) concentration and temperature occur only temporarily in Z-stabilization pathways, we may slightly relax the upper limit of the temperature rise. We can then search for a scenario with larger emissions in the 21st century; such a scenario may have potential for practical application. It is suggested that in this Z-stabilization pathway, larger emissions in the near future may be important from a socioeconomic viewpoint.(Contributed by Taroh MATSUNO, M.J.A.).     

Effects of pigments on the volume‐phase‐transition properties of N‐isopropylacrylamide gels as light‐modulation materials

The effects of pigments contained in N‐isopropylacrylamide (NIPAM) gels on their volume‐change properties were investigated. All the NIPAM gel particles, containing various kinds and concentrations of pigments, showed a volume phase transition at 34 °C. No pigment affected the volume‐phase‐transition temperature of the NIPAM gels. As the concentration of the pigment in the NIPAM gels was increased, the amount of the volume change of the NIPAM gels was reduced. The water absorptivity of the NIPAM gels in the swollen state decreased as the pigment concentration increased, whereas the water absorptivity in the shrunken state was almost constant. Reducing the initial monomer concentration of the polymerization of the NIPAM gel increased the water absorptivity in the swollen state. With an increase in the water absorptivity, the volume changes of the NIPAM gels containing pigments were increased. Prototype light modulators in which the NIPAM gel particles containing pigment were dispersed between glass plates were fabricated. The light modulator using the gel particles with improved diameter change (d/d₀ = 2.3, where d and d₀ are the equilibrium diameter and the diameter of the fully shrunken state at 50 °C, respectively) exhibited a larger transmittance change from 8 to 79% than that using the gel particles before the improvement (d/d₀ = 1.7; from 38 to 79%) according to temperature changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4644–4655, 2006     

Stereoselective total synthesis of acremomannolipin A and its anomer,the potent calcium signal modulators with a novel glycolipid structure: role of the stereochemistry at the anomeric center on the activity

A full account of stereoselective total synthesis of a novel glycolipid, acremomannolipin A (1), the potent calcium signal modulator isolated from Acremonium strictum, by employing the stereoselective β-mannosylation of 4,6-O-benzylidene-protected mannosyl sulfoxide with d-mannitol as the key reaction is described. The α-anomer (epi-1) of 1 was also synthesized selectively. The calcium modulating activity was reduced upon inversion of the configuration at the anomeric center, indicating that the β-configuration of the mannose moiety is preferable for the activity.     

Sharp Maximal Inequalities and Its Application to?Some Bilinear Estimates

In this note we establish the sharp maximal inequalities for Herz spaces and Morrey spaces by use of good ??-inequality. As an application, we obtain estimates of some bilinear forms which include usual product of functions and the nonlinear term of Euler and Navier-Stokes equations on Herz spaces and Morrey spaces.     

Transverse excitations in liquid Ga

The transverse acoustic excitation modes were detected by inelastic x-ray scattering in liquid Ga in the Q range above 9?nm^?1 although liquid Ga is mostly described by a hard-sphere liquid. An ab initio molecular dynamics simulation clearly supports this finding. From the detailed analysis for the S(Q,ω) spectra with a good statistic quality, the lifetime of 0.5 ps and the propagating length of 0.4–0.5?nm can be estimated for the transverse acoustic phonon modes, which may correspond the lifetime and size of cages formed instantaneously in liquid Ga. The microscopic Poisson’s ratio estimated from the dynamic velocities of sound is 0.42, indicating a rubber-like soft elastic property of the cages.