Effect of cyclodextrins on the thermal epimerization of tea catechins

金沢大学理工研究域物質化学系The epimerization reaction of tea catechins was investigated at pH 5.5 and 120°C in the absence/presence of cyclodextrins (CDs). In the absence of CDs, a considerable quantity (∼20%) of products originating from reactions other than the epimerization ("other products") was formed during the epimerization of gallated catechins. In the case of (-)-EGCg, addition of β-CD to the reaction solution reduced the quantity of these other products to just a few percent, but other CDs with different cavity sizes had little effect. Generally, the addition of β-CD increased the ratio of non-epi type catechins, that is, [non-epi type catechin] / ([epi type catechin]+[non-epi type catechin]). Molecular orbital (MO) calculations using the PM3 method suggested that non-epi type catechins are more thermodynamically stable than their epi-type counterparts, moving the equilibrium position in favor of non-epi type catechins in the epimerization process

Crystal structures of racemic and enantiomeric 5-isopropyl-5-methylhydantoin

Crystal structures of racemic and enantiomeric 5-isopropyl-5-methylhydantoin (IPrMH) have been determined by single crystal X-ray diffraction. Melting temperatures and solid state infrared spectra are also measured. Racemic IPrMH has a lower melting temperature than the pure enantiomer by 25 °C. The infrared spectrum of racemic IPrMH is identical with that of the pure enantiomer. Nevertheless, the racemic IPrMH doesn’t crystallize as a conglomerate but as a racemic compound. The racemic and the enantiomeric crystals are very similar to each other in molecular geometries and intermolecular interactions. In the both cases, the molecules are connected via N−H···O hydrogen bonds to form R22(8) rings, and these rings are linked into infinite one-dimensional tapes. In the racemic crystal, a single tape is composed of single enantiomer and itself is homochiral

Synthesis and crystal structure of (S)-5-isopropyl-5-methyl-2-thiohydantoin

(S)-5-Isopropyl-5-methyl-2-thiohydantoin was synthesized by one-pot reaction of α-methyl-L-valine and thiourea in the absence of solvent. The crystal structure of this compound has been determined from single crystal X-ray diffraction data. This is the first report on the crystal structure of a homochiral 5-substituted 2-thiohydantoin with the unsubstituted NH groups. This compound, C7H12N2OS crystallizes in the chiral orthorhombic space group P212121 with four molecules in the unit cell. The unit cell parameters are: a = 8.2798(12) Å, b = 8.6024(13) Å, c = 12.826(2) Å and V = 913.6(2) Å3. In the crystals, the thioamide and amide N-H of one molecule are hydrogen-bonded to the thioamide C=S group of neighboring molecules to form rings with the R22(8) graph-set motif, and these rings are linked into infinite one-dimensional tapes

Crystal structures and conformations of 5-benzyl-2-thiohydantoin and its 1-acetylated derivative

金沢大学理工研究域物質化学系The crystal structures of 5-benzyl-2-thiohydantoin (5-BTH) and 1-acetyl-5-benzyl-2-thiohydantoin (1-Ac-5-BTH) have been determined by X-ray diffraction. In the 5-BTH crystals, the enantiomeric (R)- and (S)-5-BTH molecules are connected to form cyclic dimers via the hydrogen bonds of the thioamide and the amide moieties. On the other hand, the intermolecular hydrogen bonds in 1-Ac-5-BTH crystals form an infinite chain. These differences in the hydrogen bond pattern are also discussed in the IR and Raman spectra. The ab initio molecular orbital calculations (Gaussian 03) with 6-31G(d,p) basis set were carried out for 5-BTH and 1-Ac-5-BTH to get the preferred conformation. Copyright © Taylor & Francis Group, LLC.全文公開20100

Roles of Cognitive Function on Visual Field Reliability Indices among Glaucoma Patients

This study reports the prevalence of cognitive impairment (CI) in patients attending a glaucoma outpatient clinic at a tertiary hospital. It also comprehensively assesses possible associations between CI and visual field (VF) reliability indices among glaucoma patients. The retrospective analysis included 1464 eyes from 746 subjects (mean age, 70.6 ± 11.9; 401 males and 345 females). CI was evaluated using the Mini-Cog test, revealing a suspected prevalence of 8.0% (60 out of 746) among the patients. After adjusting for various background parameters using a mixed effects regression model, an abnormal Mini-Cog score was linked to higher false negative (FN) (p = 0.0034) and false positive (FP) (p = 0.0051) but not fixation loss (FL) (p = 0.82). Among the Mini-Cog components, a lower word recall test score was associated with higher FN (p p = 0.054) and no significant effect on FL (p = 0.09). Conversely, a lower clock drawing test score was associated with higher FP (p = 0.038), while FL (p = 0.49) and FN (p = 0.12) remained unaffected. These findings suggest that CI can impact the reliability of VF testing among glaucoma patients, highlighting the importance of assessing cognitive function in glaucoma care

Spectroscopic characterization of thiol adducts formed in the reaction of 4-methylcatechol with DPPH in the presence of N-acetylcysteine

Nucleophiles such as thiol compounds have enhancing effects on the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities of polyphenols. Several authors have suggested that regeneration of the catechol structure from o-quinone plays a key role in enhanced radical scavenging activity. We therefore explored the reaction of 4-methyl catechol (MC) with DPPH in the presence of N-acetylcysteine (NACys) to clarify the mechanism underlying activity enhancement. Four types of NACys adducts were isolated and purified by preparative HPLC after the reactions reached equilibrium and their structures were characterized spectroscopically using UV-Vis absorption, NMR, and LC-MS. Oxidation of MC using a periodate resin and subsequent reaction with NACys were also studied. LC-MS analyses revealed that a mono-NACys adduct is produced as the major product in the reaction of MC quinone with NACys, and direct reduction by NACys occurs in reactions with NACys MC quinones