Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Spectrophotometric determination of nitrate and nitrite in water and some fruit samples using column preconcentration

A sensitive analytical method for the simultaneous assay of nitrate and nitrite in water and some fruit samples is presented. The method is based on nitrite determination using the diazotization-coupling reaction by column preconcentration and on the reduction of nitrate to nitrite using the Cd-Cu reductor column. Nitrite is diazotized with sulfanilamide (SAM) in the pH range 2.0-5.0, sulfamethizole (SM) in pH 1.8-5.6 and sulfadimidine (SD) in pH 1.8-4.0 in a hydrochloric acid medium to form water-soluble colourless diazonium cations. These cations were coupled with sodium 1-naphthol-4-sulfonate (NS) in the pH range 9.0-12.0 for the SAM-NS system, pH 8.6-12.0 for the SM-NS system and pH 9.4-12.0 for the SD-NS system to be retained on naphthalene-tetradecyldimethylbenzylammonium (TDBA)-iodide (I) adsorbent packed in a column. The solid mass is dissolved out from the column with 5 ml of dimethylformamide (DMF) and the absorbance is measured by a spectrophotometer at 543 nm for SAM-NS, 537 nm for SM-NS and 530 nm for SD-NS. The calibration graph was linear over 30-600 ng NO(2)-N and 22-450 ng NO(3)-N in 15 ml of final aqueous solution (i.e. 2-40 ng NO(2)-N ml(-1) and 1.5-30 ng NO(3)-N ml(-1) in aqueous sample) for three systems. The detection limits were 1.4 ng NO(2)-N ml(-1) and 1.1 ng NO(3)-N ml(-1) for SAM-NS, 1.2 ng NO(2)-N ml(-1) and 0.89 ng NO(3)-N ml(-1) for SM-NS, 1.0 ng NO(2)-N ml(-1) and 0.75 ng NO(3)-N ml(-1) for SD-NS, respectively. The concentration factor is eight for SAM-NS and SM-NS, and 12 for SD-NS. Interferences from various foreign ions have been examined and the method was successfully applied to the determination of low levels of nitrate and nitrite in water and some fruit samples.     

Selective extraction of gallium from aluminum and indium using tripod phenolic ligands

Solvent extraction of trivalent group 13 metal cations such as aluminum, gallium and indium with tripod quadridentate phenolic ligand, tris(2-hydroxy-3,5-dimethylbenzyl)amine (H(3)tdmba), was investigated as fundamental study for their mutual separation. Gallium was extracted almost quantitatively as Ga(tdmba) (logK(ex)=-6.66+/-0.06 on using chloroform as extraction solvent), whereas aluminum and indium were hardly extracted due to steric hindrance on complexation of them with the ligand. The extracted Ga species was estimated as trigonal bipyramidal complex with one H(2)O molecule. Furthermore, extractability of Ga was increased by changing the ligand to more acidic tris(5-chloro-2-hydroxy-3-methylbenzyl)amine (H(3)tcmba) (logK(ex)=-6.18+/-0.18 on using dichloroethane as extraction solvent).     

Synthesis and Antibacterial Activity of 3‐(Substituted arylmethyl)‐4‐acylaminomethyloxazolidin‐2‐ones and Derivatization to Symmetrical Twin‐Drug Type Molecules

In connection with our studies on antibacterial active compounds in the class of new oxazolidinones against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Escherichia coli) strains, some molecular modifications were attempted. In this study, molecular modifications of 4‐aminomethyloxazolidin‐2‐ones ( 3a ) to the corresponding 4‐acylaminomethyloxazolidin‐2‐one derivatives ( 3c–d ) and preparations of the represented twin‐drug type molecules ( 10–14 ) were investigated. Some additional 4‐dialkylaminomethyloxazolidin‐2‐ones ( 2 ) were also synthesized. The synthesized compounds were evaluated for antibacterial activity with Gram‐positive (S. aureus) and Gram‐negative (E. coli) strains.     

Studies on the Syntheses of Multilayered [2. 2] Paracyclophanes

It is well-known that a number of double-layered compounds such as [2. 2]paracyclophane show anomalous physical and chemical properties due to the transannular π-electronic interaction between the stacked aromatic rings.²) Moreover, the interaction significantly increases with an increase of the layers as observed in a series of multilayered [2. 2]paracyclophanes³) and thereby it is of great interest to search a possibility of an organic semiconductor or its suitable model in them or their derivatives. However, such a study has been severely limited by great difficulty on the syntheses of the layered cyclophanes. While a number of synthetic methods have been developed for cyclophanes,²) only 1,6-Hofmann elimination method has so far been adopted to the preparation of multilayered [2.2]paracyclophanes.³) In practice, however, the yield is very low and becomes markedly poor with the increasing layers. Now we have studied some practical improvements on the preparation of multilayered [2.2]paracyclophanes.     

Performance review of locking alleviation methods for continuum ANCF beam elements

Nonlinear Dynamics - The absolute nodal coordinate formulation (ANCF) is a nonlinear finite element approach proposed for the large deformation dynamics analysis of beam- and plate/shell-type...     

Formulation for XPS spectral change of oxides by ion bombardment as a function of sputtering time

XPS measurement revealed that the original state of TiO₂ was changed to Ti₂O₃ and TiO by ion bombardment. TiO₂ decreased and Ti₂O₃ increased at the initial stage. TiO increased at a later stage than Ti₂O₃. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO₂ to Ti₂O₃ and from Ti₂O₃ to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO₂ to Ti₂O₃ is about ten times larger than that from Ti₂O₃ to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment.     

Lifetime distribution and estimation problems of consecutive-k-out-of-n:F systems

Explicit formula is given for the lifetime distribution of a consecutive-k-out-of-n:F system. It is given as a linear combination of distributions of order statistics of the lifetimes of n components. We assume that the lifetimes are independent and identically distributed. The results should make it possible to treat the parametric estimation problems based on the observations of the lifetimes of the system. In fact, we take up, as some examples, the cases where the lifetimes of the components follow the exponential, the Weibull, and the Pareto distributions, and obtain feasible estimators by moment method. In particular, it is shown that the moment estimator is quite good for the exponential case in the sense that the asymptotic efficiency is close to one.This research was partially supported by the ISM Cooperative Research Program (94-ISM-CRP-5).     

Compatibility and stability tests of risperidone with soft-drinks by isothermal titration microcalorimetry

Isothermal titration microcalorimetry has been applied to investigate the compatibility testing of risperidone oral solution with soft-drinks and the interaction with tea tannin such as (–)-epigallocatechin, (–)-epicatechin, theaflavin and their gallates. In aqueous solution, risperidone was exothermically bound to tea tannin with binding affinity (10³–10⁴ M^–1), small enthalpy and entropy changes reflecting van der Waal’s interaction to form an insoluble complex at 1:1 molar ratio. The heat effect of risperidone titrated into soft-drinks containing tannin was exothermic and proportional to the quantity of the complex. While, no significant heat effect was found for risperidone titrated into a pet-bottled water and an infusion of parched barley without tea tannin. These results were agreed with stability testing of risperidone in some soft-drinks by HPLC method.