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p-Aminobenzoates (PABA) and benzophenones in cosmetic products absorb UV radiation. We have developed two simple methods to simultaneously determine whether cosmetic products contain any of eight sunscreen compounds. The first method used high-performance liquid chromatography (HPLC) and a Cosmosil 5C18-MS column with an isocratic system consisting of acetonitrile-H2O solution (60/40, v/v) acidified by 0.1% phosphoric acid (v/v); the analysis was monitored by absorbance at 254 nm with a constant flow-rate 0.8 mL/min. This method could easily determine the presence of these compounds in non-pretreated sunscreen products in 30 min. The second method employed capillary electrophoresis (CE) in buffer solution (pH 10.0) containing 20 mM borate; the same analysis was made within 10 min. Reproducibility (relative standard deviation) of the proposed methods, on the basis of the peak-area ratios in six replicate injections, was good with only a slight deviation of 0.31-0.75% (for HPLC system) and 1.65-3.55% (for CE system). The detection limit (S/N=3) of the individual marker substances varied from 0.08 to 0.87 μg/mL (for HPLC system) and 0.23 to 1.86 μg/mL (for CE system). Although the HPLC method was superior to the CE method in both reproducibility and resolution, it required longer retention time. The HPLC and CE methods developed were both successfully applied to the assay of 8 UV-absorbing agents in 11 commercial sun protection products.

The protective effect of an aqueous Pericarpium Granati extract (APG) against carrageenan-induced inflammatory damage in mice was investigated. The results showed that APG displayed radical scavenging, reducing activity, and liposome protection activity in acellular systems. The implementation of an HPLC helped identify polyphenolic components including epicatechin (11.9 mg/g), gallic acid (3.9 mg/g), ellagic acid (2.4 mg/g), ferulic acid (1.0 mg/g), quercetin (0.7 mg/g), and kaempferol (0.5 mg/g). APG administration in the range of 0.25–1.0 g/kg showed a concentration dependent inhibition on inflammatory response in carrageenan induced mice. The anti-inflammatory effects of APG could be related to the suppression of tissue nitric oxide and tumor necrosis factor-α, and associated with the reduction of lipid peroxidation and an increase in antioxidant enzyme activities including catalase, superoxide dismutase, and glutathione peroxidase in vivo. The results showed that APG might serve as a natural source of anti-inflammatory and antioxidative compounds in vivo.

In this study, the effects of a water extract of Flos Inulae (WFI) on antioxidant, antimutation and antityrosinase were investigated. The results showed that WFI inhibited the mutagenicity of 2-aminoanthracene (2-AA), an indirect mutagen; and 4-nitroquinoline-N-oxide (4-NQO), a direct mutagen toward Salmonella typhimurium TA 98 and TA 100. In addition, WFI, in the range of 0.2–0.6 mg/ml, showed radical scavenging, reducing activities and chelating activity as well as decreased lipid oxidative damage. Meanwhile, WFI also inhibited tyrosinase activity and NO generation in lipopolysaccharide (LPS) stimulated macrophages. High performance liquid chromatography analysis suggests that the major phenolic constituents in WFI are chlorogenic acid, rutin, quercetin, luteolin and kaempferol. These bioactive components may contribute to the protective effects of WFI. The obtained data suggests that Flos Inulae can be applied to antimutation, antityrosinase and anti-inflammation.

The antioxidant and antityrosinase activities of the water extract ofFlemingia macrophyllaroot (WEFM) were investigated. The results showed that WEFM exhibited radical scavenging and reducing activities, as well as ferrous ion chelating property. In addition, WEFM also protected phospholipids against oxidation, indicating that WEFM could protect biomolecules from oxidative damage. Meanwhile, in the range of 50–100 μg/mL, the tyrosinase inhibitory activity of WEFM increased with an increase in sample concentration and was superior to that of the water extract ofGlycine tomentellaroot (WEGT). A high performance liquid chromatography analysis was used to determine the phenolic components, revealing that daidzin, daidzein, genistin, and genistein were present in WEFM and WEGT. Acting as an antioxidant and a tyrosinase inhibitor, these bioactive constituents could contribute to the protective effects of WEFM. Overall, the results showed that WEFM might serve as a natural antioxidant and tyrosinase inhibitor.

In this study, the effects of four molasses related products including cane molasses (CM), carob molasses (CAM), grape molasses (GM), and sorghum molasses (SM) on the antimutation and nitric oxide (NO) production were examined. The results showed that the four molasses products, particularly CAM, inhibited the mutagenicity of 2-aminoanthracene (2-AA), an indirect mutagen; and 4-nitroquinoline-N-oxide (4-NQO), a direct mutagen in Salmonella typhimurium TA98 and TA100. In addition, CAM also showed a higher ABTS radical inhibition, reducing activity, and decreasing lipid oxidative damage more than the others kinds of molasses. In the range of 0–0.8 mg/ml, the inhibitory effect of all molasses products on NO generation in lipopolysaccharide (LPS) stimulated macrophages increased with increasing concentrations, and CAM showed the best inhibition of NO production. These data suggested that the four molasses related products display their biological activities in terms of antioxidation, antimutation, and anti-inflammation.

Various 4,5-disubstituted-3-sulfonyl glutarimides 3 were synthesized from α-sulfonyl acetamide 1 and ethyl α,β-disubstituted acrylate esters 2 via stepwise facile [3+3] annulation in moderate yield. The synthesis of pyridin-2-one 9, a key intermediate for mappicine ketone (4) synthesis, was also reported.

A formal total synthesis of the iridoid monoterpene (′) -dimethyl secologanoside (6) is described. The Norrish 1 type fragmentation ofbicyclo[2.2.1]heptannone 9 is the key step.

The synthesis of cyclopentanoid natural products, iridoid monoterpenes and prostaglandins, was achieved from a common intermediate 2, which was obtained from 1 via photochemical rearrangement.

A formal [3+3] cycloaddition strategy to substituted glutarimides was studied. N -Benzyl α-sulfonylacetamides and various α,β-unsaturated esters were used as starting materials.

A formal total synthesis of 10-deoxygeniposide (4), Mussaenoside (5), and 8-epi-loganin (6) from a versatile diquinane 3 is described.

The chemoselectivity in the palladium-catalyzed intramolecular cyclization of 2-(o-bromoaryl)-alkenenitriles depends on the nature of α-substitutents. 2-(o-Bromoanilino)alkenenitriles attacked the cyano group, followed by the cyano group transposition and hydrolysis, to give o-(methylamino)benzonitrile. 2-(o-Bromobenzyl)alkenenitriles, 2-(o-bromophenylthio)alkenenitriles and 2-(o-bromophenoxy)-alkenenitriles attacked the olefinic double bonds and led to l-vinyl-2-indancecarbonitrile, 1,2,3,4-tetrahydronaphthalene-2-carbonitriles, 3,4-dihydro-2H-benzo[b]thiine-2-carbonitriles, and 3,4-dihydro-2H-benzo[b]oxine-2-carbonitriles. A general mechanism for the palladium-catalyzed arylations is proposed.

A total synthesis of (±)-iridolactone (1) from bicyclo[2.2.1]ketone 6 is described. Trisubstituted cyclopentenoid aldehyde 7 is a key intermediate.

A total synthesis of (±)-boschnialactone (1) and (±)-tertahydroanhydrodesoxyaucubigenin (2) is described and trisubstitued cyclopentenoid 3 is a key intermediate.

α-(o-Bromoanilino)alkenenitriles 1a–f and 2a–e and α-(N-alkenylamino)-β-(o-bromophenyl)propanenitrile 7a–c< and 8a–c undergo palladium-catalyzed conversion into o-(methylamino)benzonitrile 12, o-[(alkenylamino)ethenyl]benzonitriles 24a–c, N-alkenylanilines 26b, 26c, 3-benzazepines 29a, 29c, 31a and 32a, γ-carbolines 36 and pyrrolo[3,2-b]indole 45. The reactions involve intramolecular additions of arylpalladium to the cyano group and subsequent processes such as cyano group transposition, hydrolysis, electrocyclization, ethyl group transfer and oxidative aromatization. A general mechanism for the palladium-catalyzed arylation of a cyano group is proposed.

This study investigated the antioxidative and anti-inflammatory activities of aqueous extracts of Schizonepeta tenuifolia Briq. (STE). The results showed that STE displayed radical scavenging and reducing activity, as well as liposome protection activity. In addition, the implementation of an HPLC with a photodiode array detector helped to identify polyphenolic components including hesperidin, luteolin, and diosmetin. STE administration in the range of 125-500 mg/kg showed concentration dependent inhibition on carrageenan induced inflammatory response in mice. The anti-inflammatory effects of STE could be related to tissue NO and tumor necrosis factor a (TNF-α) suppression, and associated with the reduction of lipid peroxidation and an increase in antioxidant enzyme activities including catalase, superoxide dismutase, and glutathione peroxidase in vivo. Overall, the results showed that STE might serve as a natural inhibitor of oxidation and inflammation.

α-(o-Bromoanilino)alkenenitriles 1a–f and 2a–e and α-(N-alkenylamino)-β-(o-bromophenyl)propanenitrile 7a–c< and 8a–c undergo palladium-catalyzed conversion into o-(methylamino)benzonitrile 12, o-[(alkenylamino)ethenyl]benzonitriles 24a–c, N-alkenylanilines 26b, 26c, 3-benzazepines 29a, 29c, 31a and 32a, γ-carbolines 36 and pyrrolo[3,2-b]indole 45. The reactions involve intramolecular additions of arylpalladium to the cyano group and subsequent processes such as cyano group transposition, hydrolysis, electrocyclization, ethyl group transfer and oxidative aromatization. A general mechanism for the palladium-catalyzed arylation of a cyano group is proposed.

Sodium borohydride regioselectively reduced various 3-sulfonyl glutarimides 1 to hydroxy piperidones 2, which were further dehydrated to 3,4-dihydro-5-sulfonylpyridin-2-ones 3 in the presence of boron trifluoride. Formal synthesis of 8a-epi-dendroprimine (4) possessing an indolizidine ring system has been accomplished via intramolecular radical cyclization of cyclic vinyl sulfone 5.

The antioxidant and antityrosinase activities of the ethanolic extract of mulberry twigs (EEMT) were investigated. The results showed that EEMT exhibited radical scavenging and reducing activity, as well as ferrous ion-chelating activity. In addition, EEMT also protected phospholipids against free radicals, indicating that EEMT could protect biomolecules from oxidative damage. Meanwhile, in the range of 0-60 μg/ml, the tyrosinase inhibitory activity of EEMT increased with increase in sample concentration, and was superior to that of the ethanolic extract of mulberry root bark (EEMR). High-performance liquid chromatography (HPLC) analysis was employed to determine the phenolic components, revealing that maclurin, rutin, isoquercitrin, resveratrol, and morin were present in EEMT. Acting as an antioxidant and a tyrosinase inhibitor, these bioactive constituents could contribute to the protective effects of EEMT. Overall, the results showed that EEMT might serve as a natural antioxidant and tyrosinase inhibitor.

N,N-Dimethylformamide (DMF) has been widely used in industries because of its extensive miscibility with water and solvents. Its health effects include hepatotoxicity and male reproductoxicity, possibly linked with mitochondrial DNA (mtDNA) alterations including mtDNA common deletion (DeltamtDNA(4977)) and mtDNA copy number. The relationship between DMF exposure and mtDNA alterations, however, has not been postulated yet. The purposes of this study were to investigate whether the DMF exposure is associated with DeltamtDNA(4977) and mtDNA copy number and to evaluate the DMF-derived mtDNA alterations are more associated with exposure to the airborne DMF concentrations or to the levels of two urinary DMF biomarkers of N-methylformamide (NMF) and N-acetyl-S-(N-methylcarbamoryl) cysteine(AMCC). Thirteen DMF-exposed workers and 13 age and seniority-matched control workers in a synthetic leather factory were monitored on their airborne DMF, NMF and AMCC in the urine as well as DeltamtDNA(4977) and mtDNA copy number in blood cells. We found that the frequencies of relative DeltamtDNA(4977) in DMF-exposed group were significantly higher than those in the control group. Moreover, elevation in the proportion of DeltamtDNA(4977) of individuals with high urine AMCC (U-AMCC) and airborne DMF levels were significantly higher than those without. We conclude that long-term exposure to DMF is highly associated with the alterations of mtDNA in urine and blood cells. The DeltamtDNA(4977) was more significantly related to repeated exposure to DMF and mtDNA copy number was more closely related to short-term DMF exposure. We also confirmed that U-AMCC is more appropriate to serve as a toxicity biomarker for DMF exposure than U-NMF. Further study with a larger number of subjects is warranted.

A formal total synthesis of (±)-verbenalol 1 and (±)-udoteatrial 2 is described. Tie key intermediate is diiodolactone 7.

A formal [3+3] cycloaddition strategy to substituted glutarimides was studied. N -Benzyl α-sulfonylacetamides and various α,β-unsaturated esters were used as starting materials.

A total synthesis of the iridoid monoterpene (±)-hop ether (2) is described. The Norrish I type fragmentation of bicyclo[2.2.1]heptanone (5) is the key step.

A synthesis of lupinine (la) is performed from 5-amino-1-pentanol in ten steps. The glutarimide (3) was obtained from 1-(5-hydroxypentyl)-2-(4-methylphenylsulfonyl)acetamide (5) and acrylate (4) via a formal [3+3] annulation. This formation of quinolizidine skeleton was established via a key acid-catalyzed cyclization method.