Measurement of adenine nucleotide levels with an adenine analyser as an index of freshness of porgy

In a prototype of an adenine analyser, adenosine and adenine nucleotides were derivatized with a fluorescent reagent, bromoacetaldehyde, after separation on a Hitachi gel No. 3012-N column by high-performance liquid chromatography. The previous analyser was improved by using a shorter reaction coil and by introduction of a Hitachi gel No. 3013-N with 5-microns particles of porous polystyrene-divinylbenzene, and applied to estimate the freshness of porgy. Total amounts of ATP, ADP and AMP in an isolated muscle just after death gradually decreased to 60% of the original amount after 5 h, and the ATP content rapidly decreased to 20% after 1 h. A good correlation was found between the levels of total adenine compounds and the energy charge values obtained from nineteen porgies frozen at a prerigour state. On the other hand, there existed no relationship between total adenine levels and the K values, which were indices for estimating freshness of fish. The analyser will be useful to evaluate the freshness of tissues and cells based on the higher contents of total adenine compounds, especially ATP.     

Improved determination of milk oligosaccharides using a single derivatization with anthranilic acid and separation by reversed-phase high-performance liquid chromatography

An improved analytical scheme for human milk neutral oligosaccharides determination was developed, in which, the oligosaccharides were pooled in two fractions (pools 1 and 2) after gel filtration, and then were quantitatively derivatized with a single fluorescent reagent, 2-anthranilic acid. Separation was by reversed-phase HPLC on an ODS-100Z column with a mobile phase of 50 mM ammonium acetate pH 4.0 and 150 mM citrate buffer pH 4.5 and monitored by a fluorescence detector at 360 nm excitation and 425 nm emission wavelengths. The method improved on the separation of neutral tetra- and hexa-saccharide isomers, namely, lacto-N-tetraose (LNT) and lacto-N-neotetraose (LNnT) as well as of lacto-N-difucohexaose I (LNDFH I) and lacto-N-difucohexaose II (LNDFH II). The separation of trisacccharide isomers, 3-fucosyllactose (3-FL) and 2′-fucosyllactose (2′-FL) was also successful. Limits of detection and quantification were in the range of 1–10 ng/l and 2–30 ng/l, respectively. The methods’ accuracy was good with its precision at <20% RSD and <1% RSD, respectively, for oligosaccharide concentration and retention time. The recoveries were in the range of 80–100%. This method was successfully applied to the separation and determination of representative neutral oligosaccharide contents in Samoa women milk.     

James-Stein estimators for time series regression models

The least squares (LS) estimator seems the natural estimator of the coefficients of a Gaussian linear regression model. However, if the dimension of the vector of coefficients is greater than 2 and the residuals are independent and identically distributed, this conventional estimator is not admissible. James and Stein [Estimation with quadratic loss, Proceedings of the Fourth Berkely Symposium vol. 1, 1961, pp. 361-379] proposed a shrinkage estimator (James-Stein estimator) which improves the least squares estimator with respect to the mean squares error loss function. In this paper, we investigate the mean squares error of the James-Stein (JS) estimator for the regression coefficients when the residuals are generated from a Gaussian stationary process. Then, sufficient conditions for the JS to improve the LS are given. It is important to know the influence of the dependence on the JS. Also numerical studies illuminate some interesting features of the improvement. The results have potential applications to economics, engineering, and natural sciences.     

Construction of Chiral Tri‐ and Tetra‐Arylmethanes Bearing Quaternary Carbon Centers: Copper‐Catalyzed Enantioselective Propargylation of Indoles with Propargylic Esters

Copper‐catalyzed enantioselective propargylation of indoles with propargylic esters and sequential Huisgen cycloaddition with azides lead to the construction of chiral triarylmethanes, bearing a quaternary carbon center, with high to excellent enantioselectivities. The result described herein can be used in the enantioselective preparation of a tetraarylmethane.     

Cycloaddition reaction of pyrimidine-dienols with dienophiles. A new approach to quinazolines

A new synthetic approach to quinazolines bearing a carboxy group is described. Reaction of 5-carbonyl substituted 1,3,6-tri-methyluracils (I) with dimethyl acetylenedicarboxylate or electron-deficient olefines affords quinazoline derivatives (III-VI) $\text{via}$ pyrimidine(Z)-dienols (II) formed by base-catalyzed isomerization.     

A comparative vibrational and NMR study of cis-cinnamic acid polymorphs and trans-cinnamic acid

The IR and Raman spectra of the two polymorphic forms (58 degree- and 68 degree-forms) of cis-cinnamic acid were measured, and the spectral differences discussed on the basis of the crystal structures of the two forms. The IR bands related to the COOH group differ in the frequencies and band shape, reflecting differences in the hydrogen bonding between the two modifications. These spectra were compared with those of trans-cinnamic acid. The IR, Raman, and NMR spectra of the isotopic compounds, including the deuterated and 13C analogs of the cis and trans acids, were also recorded in the solid state and in solution to confirm the spectral assignments.