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.     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.     

Cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia for chiral separation in high performance liquid chromatography.

Porous zirconia particles are very robust material and have received considerable attention as a stationary phase support for HPLC. We prepared cellulose dimethylphenylcarbamate-bonded carbon-clad zirconia (CDMPCCZ) as a chiral stationary phase (CSP) for separation of enantiomers of a set of 14 racemic compounds in normal phase (NP) and reversed-phase (RP) liquid chromatography. Retention and enantioselectivity on CDMPCCZ were compared to those on CDMPC-coated zirconia (CDMPCZ) to see how the change in immobilization method of the chiral selector affects the retention and chiral selectivity. In NPLC, retention was longer and the number of resolved racemates was smaller on CDMPCCZ than on CDMPCZ. However, chiral selectivity factors for some resolved racemates were better on CDMPCCZ than on CDMPCZ. The longer retention on CDMPCCZ is likely due to strong, non-chiral discriminating interactions with the carbon layer on CDMPCZ. In RPLC only two racemates were resolved on CDMPCCZ, but retention times were shorter than, and resolutions were comparable to, those in NPLC, indicating a potential for improving chromatographic performance of the CDMPCCZ column in RPLC with optimized column preparation and separation conditions.     

Unsaturated bond existing in tetrafluoroethylene-propylene-vinylidene fluoride terpolymer

Infrared and nuclear magnetic resonance (NMR) spectroscopies have been applied for quantitative comparison on unsaturated bonds in tetrafluoroethylene (TFE)-propylene (P)-vinylidene fluoride (VdF) terpolymers. These spectroscopies have led to consistent results while they are based on completely different principles. It is shown that the absolute concentration can be evaluated from NMR measurements. The behavior of unsaturation has been discussed in terms of after-treatment such as wet and dry treatments. The result obtained here can give the important information to improve the performance of fluoroelastomer based on TFE-P-VdF terpolymers.     

Toeplitz operators associated with analytic crossed products II (invariant subspaces and factorization)

In [16], we introduced the notion of Toeplitz operators associated with analytic crossed products. In this paper, we study the structure of invariant subspaces with respect to the analytic crossed products. We also investigate the inner-outer factorization problems for analytic Toeplitz operators, the factorization problem for non-negative Toeplitz operators and Szegö's infimum problem.This work was supported in part by a Grant-in-Aid for Scientific Research from the Japanese Ministry of Education.     

Validation of a method for predicting the precision, limit of detection and range of quantitation in competitive ELISA.

The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.     

On K1 and K2 of Algebraic Surfaces

In this paper we study higher Chow groups of smooth, projective surfaces over a field k of characteristic zero, using some new Hodge theoretic methods which we develop for this purpose. In particular we investigate the subgroup of CH ^r+1 (X,r) with r = 1,2 consisting of cycles that are supported over a normal crossing divisor Z on X. In this case, the Hodge theory of the complement forms an interesting variation of mixed Hodge structures in any geometric deformation of the situation. Our main result is a structure theorem in the case where X is a very general hypersurface of degree d in projective 3-space for d sufficiently large and Z is a union of very general hypersurface sections of X. In this case we show that the subgroup of CH ^r+1 (X,r) we consider is generated by obvious cycles only arising from rational functions on X with poles along Z. This can be seen as a generalization of the Noether–Lefschetz theorem for r = 0. In the case r = 1 there is a similar generalization by Müller-Stach, but our result is more precise than it, since it is geometric and not only cohomological. The case r = 2 is entirely new and original in this paper. For small d, we construct some explicit examples for r = 1 and 2 where the corresponding higher Chow groups are indecomposable, i.e. not the image of certain products of lower order groups. In an appendix Alberto Collino constructs even more indecomposable examples in CH ³ (X,2) which move in a one-dimensional family on the surface X.Contribution to appendix.