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.     

Generalized binomial and negative binomial distributions of order<Emphasis Type="Italic">k</Emphasis> by the<Emphasis Type="Italic">l</Emphasis>-overlapping enumeration scheme

In this paper, we investigate the exact distribution of the waiting time for ther-th ℓ-overlapping occurrence of success-runs of a specified length in a sequence of two state Markov dependent trials. The probability generating functions are derived explicitly, and as asymptotic results, relationships of a negative binomial distribution of orderk and an extended Poisson distribution of orderk are discussed. We provide further insights into the run-related problems from the viewpoint of the ℓ-overlapping enumeration scheme. We also study the exact distribution of the number of ℓ-overlapping occurrences of success-runs in a fixed number of trials and derive the probability generating functions. The present work extends several properties of distributions of orderk and leads us a new type of geneses of the discrete distributions.     

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.     

Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.     

Establishment of hybrid-derived offspring populations in the Ohomopterus ground beetles through unidirectional hybridization

An approach to deduce the mechanism of stabilization of the hybrid-derived populations in the Ohomopterus ground beetles has been made by comparative studies on the phylogenetic trees of the mitochondrial and nuclear DNA. A phylogenetic tree based on the internal transcribed spacer (ITS) of nuclear ribosomal gene roughly reflects the relations of morphological species group, while mitochondrial NADH dehydrogenase subunit 5 (ND5) gene shows a considerable different topology on the tree; there exist several geographically-linked lineages, most of which consist of more than one species. These results suggest that the replacement of mitochondria has occurred widely in the Ohomopterus species. In most cases, hybridization is unidirectional, i.e., the species A (♂) hybridized with another species B (♀) and not vice versa, with accompanied replacement of mitochondria of A by those of B. The results also suggest that partial or complete occupation of the distribution territory by a hybrid-derived morphological species. The morphological appearance of the resultant hybrid-derivatives are recognized as that of the original species A. Emergence of a morphological new species from a hybrid-derived population has been exemplified.     

Diamagnetic muon yields of metal acetylacetonates

Diamagnetic muon yields /P_D/ in various metal acetylacetonates were measured at room temperature by the muon spin rotation technique. We have found a clear difference in P_D between complexes of typical elements and those of transition elements. We suggest that partially filled inner orbitals play some important role in determining the diamagnetic yield in these complexes.     

Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

Femtosecond intermolecular electron transfer in condensed systems

We have investigated the ultrafast intermolecular electron transfer (ET) from an electron-donating solvent (aniline (AN) or N, N-dimethylaniline (DMA)) to an excited dye molecule (oxazines (Nile blue and oxazine 1) or coumarins). A non-exponential time dependence was observed in AN and can be explained by solvent reorientation and nuclear motion of the reactants. However, in DMA, a single exponential process was observed for Nile blue (160 fs) and oxazine 1 (280 fs), which can be explained by assuming that the rate of ET is limited mainly by ultrafast nuclear motion. A clear substituent effect on intermolecular ET was observed for the 7-aminocoumarins. When the alkyl chain on the 7-amino group is extended and a hexagonal ring with the benzene moiety is formed, the rate of ET is reduced by three orders of magnitude. This effect can be explained by a change in the free energy difference of the reaction and by the vibrational motion of the amino group.