Decarboxylative Aldol Reaction of α,α-Difluoro-ß-keto Esters: Easy Access to Difluoroenolate.

Yb(OTf)3 promoted the Krapcho decarboxylation of 2,2-difluoro-3-oxopropanoate, and a subsequent aldol reaction was achieved. This process is the first example of generating difluoroenolates through a decarboxylation-type process, and a large number of carbonyl compounds are applicable to the aldol reaction. The protocol is a complete one-pot reaction that uses the bench-stable and nonhygroscopic 2,2-difluoro-3-oxopropanoate to generate the difluoroenolate. This strategy has been applied for the synthesis of CF2-containing bioactive GABAB agonists, contributing to drug design.

Shock-absorbing effect of flooring-adopted mechanical metamaterial technology and its influence on the gait and balance of older adults.

OBJECTIVE: To elucidate the performance of a shock-absorbing floor material with a mechanical metamaterial (MM-flooring) structure and its effect on the gait and balance of older adults. METHODS: The drop-weight impact was applied to evaluate the shock-absorbing performance. The falling weight was adjusted equivalent to the energy exerted on the femur of an older woman when she falls, which was evaluated on the MM-flooring and six other flooring materials.Nineteen healthy people over the age of 65 years participated in the gait and balance evaluations. The timed up and go and two-step tests were adopted as gait performance tests, and the sway-during-quiet-balance test with force plates and the functional reach test (FRT) were adopted as balance tests. All the participants underwent these tests on the MM-flooring, shock-absorbing mat and rigid flooring. RESULTS: The shock-absorbing performance test revealed that MM-flooring has sufficient shock-absorbing performance, and suggesting that it may reduce the probability of fractures in the older people when they fall. The results of the gait performance test showed that the participants demonstrated the same gait performance on the MM-flooring and the rigid floor. In the quiet standing test, MM-flooring did not affect the balance function of the participants to the same extent as the rigid floor, compared with the shock-absorbing mat. In the FRT, no significant differences were found for any of the flooring conditions. CONCLUSIONS: MM-flooring has the potential to prevent fractures attributed to falls and does not affect the gait or balance of older adults.

Effect of maternal Chlorella supplementation on carotenoid concentration in breast milk at early lactation.

Breast milk carotenoids provide neonates with a source of vitamin A and potentially, oxidative stress protection and other health benefits. Chlorella, which has high levels of carotenoids such as lutein, zeaxanthin and ß-carotene, is an effective dietary source of carotenoids for humans. In this study, the effect of maternal supplementation with Chlorella on carotenoid levels in breast milk at early lactation was investigated. Ten healthy, pregnant women received 6 g of Chlorella daily from gestational week 16-20 until the day of delivery (Chlorella group); ten others did not (control group). Among the carotenoids detected in breast milk, lutein, zeaxanthin and ß-carotene concentrations in the Chlorella group were 2.6-fold (p = 0.001), 2.7-fold (p = 0.001) and 1.7-fold (p = 0.049) higher, respectively, than those in the control group. Our study shows that Chlorella intake during pregnancy is effective in improving the carotenoid status of breast milk at early lactation.

Concentrations of organochlorine pollutants in mothers who gave birth to neonates with congenital hypothyroidism.

We have investigated the effects of prenatal exposure to dioxin-like compounds (PCDDs, PCDFs and dioxin-like PCBs), PCBs and organochlorine pesticides (DDT, HCH, chlordane, HCB and their metabolites) on the incidence of congenital hypothyroidism and/or cretinism in Fukuoka, Japan from 2001 to 2004. Thirty-four positive neonates of the mass-screening for cretinism were classified into three groups by the pediatrician after the reevaluation of the serum TSH level, that is, negative in reevaluation group, hyper thyroid stimulating hormone (TSH) emia group and cretinism group. One-hundred and two negative neonates of the mass-screening were classified into the normal group. Concentrations of these organochlorine compounds in the breast milk of mothers, which were considered as the indicator of prenatal exposures to them, were gradually increased from the normal group to the cretinism group in the four groups and were around two times higher in the cretinism group than in the normal group. According to the case-control study adjusted for the parity and mother's age, odds ratios of PCBs, DDT and HCB were 10 (p=0.003), 10 (p=0.003) and 22 (p=0.004), respectively and in dioxin-like compounds, PCDFs showed the highest odds ratio, 9.8 (p=0.005). Based upon those findings, these compounds seemed play an important role in the incidence and/or causation of the cretinism.

Contamination status of persistent organochlorines in human breast milk from Japan: recent levels and temporal trend.

Contamination levels of persistent organochlorines (OCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), dichlorodiphenyltrichloroethane and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), and chlordane compounds (CHLs) was examined in human breast milk collected during 2001-2004 from Fukuoka prefecture in Japan. The concentrations of OCs such as dioxins and related compounds, DDTs, CHLs and HCB in human breast milk from primiparae were comparable to or slightly higher than the data obtained during 1998, indicating that the levels of these contaminants in Japanese human breast milk have not decreased since 1998 and Japanese are continuously exposed to these chemicals, presumably via fish intake. In addition, OC levels in human breast milk from primiparae were significantly higher than those from multiparae, implying elimination of OCs via lactation. Furthermore, significant positive correlations were observed between levels of OCs in human breast milk and the age of primiparae. These results indicate that the mothers with higher age may transfer higher amounts of OCs to the first infant than to the infants born afterwards through breast-feeding, and hence the first born children might be at higher risk by OCs.