Consecutive determination of rutin and quercetin by spectrophotometric measurements

The consecutive determination of rutin and quercetin without any pretreatment for separation was examined in methanol solutions by a conventional and a two-wavelength spectrophotometry. Based the tendency of quercetin to form more stable metal complexes compared to rutin, quercetin can be determined through the tin(II) complex formation without interference from rutin. The method was applied to the determination of quercetin in the concentration range of 3.0 × 10^?6 to 2.0 × 10^?5M.Quercetin is apt to be oxidized by oxygen rather than rutin, especially in the presence of copper(II), whereas rutin is not decomposed under such a condition. After removal of quercetin through copper(II)-catalyzed oxidation, rutin ranging in concentration from 2.0 × 10^?6 to 2.0 × 10^?M was determined by the absorbance measurement of rutin-copper(II) complex in slightly alkaline methanol media.Both rutin and quercetin were determined directly by two-wavelength spectrophotometry, without adding any complex forming metals; the lower limit of detection was about 1.0 × 10^?5M. The method was extended to the determination of a smaller amounts of rutin and quercetin using the absorption peaks of their zirconium(IV) complexes, and the determination of both components in the range of 5.0 × 10^?6 to 3.0 × 10^?5M was made with a relative error of within ±4%.     

Application of Rh-catalyzed cyclization to the formation of a chiral quaternary carbon

Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3,3,4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3,3,4-cis-trisubstituted cyclopentanones (+/-)-7a,b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]CIO4 afforded 3,3,4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed.     

A density functional study on hydrated clusters of orthoboric acid, B(OH)3(H2O)n (n=1–5)

We have calculated the optimized structures and stabilization energies for hydrated clusters of orthoboric acid molecule, B(OH)₃(H₂O)_n (n=1–5), with a hybrid density functional approach. Although some ion-pair structures are revealed in the case of n=4 and 5 clusters, the most stable structure is found to be a non-proton-transferred form up to n=5 hydrated clusters. The calculated IR spectra of the stable B(OH)₃(H₂O)_n of n=3–5 clusters predict small red shifts of hydrogen-bonded OH frequencies. These geometry and IR results are related to the weak acidity nature of orthoboric acid.     

Optical observation of gas bridging between hydrophobic surfaces in water

The very strong and long-ranged interaction force between hydrophobic surfaces in water has been a debated issue for a long time. Recent studies suggest that the long-range attraction is attributable to the bridging of nanoscopic bubbles attached on the surfaces. However, it is still unclear at present whether such a bridging is able to exit stably or not. To clarify the existence of the gas bridge, we conducted the optical observation and the force measurement between the hydrophobic glass particle and plate in water simultaneously, using a combined apparatus of an atomic force microscope and an optical inverted microscope. It is found that (i) the image of the dark ring of ca. 1 mum in diameter appears in the region where the existence of the bridge is confirmed by force curves, but disappears when the separation between surfaces becomes shorter than the low limit of the wavelength of visible light, and (ii) the sudden disappearance of the image coincides well with the breakage of the bridge estimated from the separating force curve. The results obtained here are consistent with the above-mentioned mechanism for the long-range attraction between hydrophobic surfaces in water.     

Ab initio theory for treating local electron excitations in molecules and its performance for computing optical properties

In this article, as a first step to develop an efficient approximation for predicting the molecular electronic excited state properties at ab initio level, we propose local excitation approximation (LEA). In the LEA scheme, the only local electron excitations within selected substructure (Chromophore) are treated to calculate the targeted excited state wavefunctions, whereas the other electron excitations (local electron excitations in other substructure and charge‐transfer excitations between different regions) are simply discarded. This concept is realized by using the localized molecular orbitals (LMO) localizing on the chromophore substructure. If the targeted transitions show the strong local character and the adequate substructure is selected as chromophore region, the LEA scheme can provide excited state properties without large loss of accuracy. The fatal slowdown of convergence speed of Davidson's iterative diagonalization due to the use of LMO can be avoided by additional transformation of LMOs. To assess the accuracy and efficiency of the LEA scheme, we performed test calculations using various compounds at configuration interaction single (CIS) and time‐dependent Hartree‐Fock (TDHF) level of theory. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Deconvolution of background-subtracted shift-and-add image by a modeled point-spread-function

Shift-and-add (SAA) is a simple method for celestial speckle imaging. However, the raw SAA-image, a direct output of the SAA operations, is not useful, because a seeing-dependent huge background is superimposed on the high-resolution image of the object. To obtain the latter, a background subtraction (BGS) is applied on the raw SAA-image. The BGS-image so obtained includes negativities due to an over-subtraction that causes brightnesses of the object’s image biased downward. The negativity in the BGS-image can be removed by a deconvolution with a point-spread-function (PSF) that has negative values. In this paper, we model the PSF with a shape that possesses peak and concave portions, and perform a deconvolution by iteratively estimating the object’s image and the model parameters. The simulated experiment has shown that the present algorithm can restore the object’s image with unbiased brightnesses. Processing the observed speckle data of Io (a Jupiter satellite) by the present method has yielded a feasible Io image with reduced negativities.