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We sought to investigate the effect of extracts from Rosa gallica petals (RPE) on skin whitening and anti-wrinkle activity. Tyrosinase activity was attenuated by RPE treatment, concomitant with the reduction of melanin accumulation in human B16F10 melanoma. Treatment of the facial skin of volunteers in a clinical trial with an RPE-containing formulation enhanced skin brightness (L* value) significantly. The underlying mechanism responsible was determined to be associated with mitogen-activated protein kinase (MAPK) activation. In addition, RPE exhibited anti-wrinkle formation activity of human dermal fibroblasts by suppressing matrix metalloproteinase (MMP)-1 level. In vivo study, RPE also inhibited solar ultraviolet-stimulated MMP-1 level by c-Jun regulation. Overall, our findings indicate that RPE evokes skin whitening and anti-wrinkle formation activity by regulating intracellular signaling, supporting its utility as an ingredient for skin whitening and anti-wrinkle cosmetic products.

In this study, we evaluated the effects of anacardic acid (AA), a phenolic lipid found in cashew nuts (Anacardium occidentale), on metabolic disorders related to obesity, fatty liver disease, and diabetes using both in vitro and in vivo models. The application of AA led to a reduction in lipid accumulation in 3T3‐L1 cells without observable cytotoxicity. Results from Western blot analysis revealed that AA treatment also led to decreased expression of fatty acid synthase and peroxisome proliferator‐activated receptor gamma. In vivo studies were performed to evaluate the effects of AA treatment on fatty liver disease and diabetes. Mice fed a high‐fat and high‐sucrose diet had significantly higher body and liver weights, and higher levels of liver fat, cholesterol, fasting glucose, and homeostasis model assessment of insulin resistance (HOMA‐IR). However, 12 weeks of oral treatment with 500 μg/kg BW AA slowed down lipid accumulation rates in the liver and mitigated insulin resistance in these mice. Thus, AA may reduce lipid levels and have an antidiabetic effect., Anacardic acid inhibits lipid accumulation in 3T3‐L1 cells. Anacardic acid reduces lipid accumulation in mice fed high‐fat and high‐sucrose diet. Anacardic acid mitigates insulin resistance in mice fed high‐fat and high‐sucrose diet.

The anti-skin inflammatory activities of rose petal extracts have been described in our previous study. Because skin inflammation is closely linked to skin aging, our study investigated the effects of Rosa gallica petals on skin aging-related activities such as skin whitening and anti-wrinkle properties. Each sample was prepared via extraction using different ethanol ratios with the objective of evaluationg optimal extraction conditions for industrial application. Aqueous 50% (v/v) EtOH extract of R. gallica petal significantly suppressed tyrosinase activity, melanin production, and solar UV-induced matrix metalloproteinase-1, a hall mark of wrinkle formation. In addition, the aqueous 50% (v/v) EtOH extract showed the highest antioxidative effect and had highest flavonoid contents, consistent with the reported anti-aging effects. Overall, our findings suggest that R. gallica petals extracts exhibit anti-aging effects. Furthermore, 50% EtOH extraction, in particular, was optimal for the highest anti-aging, and anti-oxidative effects as well as to obtain the highest flavonoid content.

This study suggests sulfuretin as an ant-skin aging agent. Sulfuretin significantly reduces solar UV (sUV)-increased matrix metalloproteinase-1 (MMP-1) expression and c-Jun phosphorylation in human dermal fibroblasts as well as skin tissue. An examination of the underlying mechanisms showed that sUV-activated MAPK signaling pathways are blocked by sulfuretin. Interestingly, sulfuretin directly inhibits the kinase activity of selected Src family. Because the amino acid sequence of Hck kinase which used kinase array is 230–497, it was assumed that sulfuretin interacts with this conserved domain of Src family kinase. It was also found that sulfuretin directly binds to sulfuretin with the lowest binding energy of −8.9 kcal/mol and free energy of −10.07 kcal/mol. Additionally, Hck protein was precipitated with sulfuretin-conjugated Sepharose 4B beads in HDFs cell lysate. Overall, present findings indicated that sulfuretin plays the role of anti-skin aging agent by acting as a general Src family kinase inhibitor in human skin.

The aim of this study was to investigate the skin anti‐inflammatory activity of rose petal extract (RPE) and the mechanisms underlying this phenomenon. Recently, flowers have been considered as dietary resources owing to their biological activities, such as inhibition of nephritis and hemorrhoids. The Rosa plant exerts various biological functions, including antioxidant and anti‐microbiological activities. Herein, we confirmed the skin anti‐inflammatory activity of RPE upon solar UV (sUV) exposure. RPE reduced sUV‐induced COX‐2 expression as well as expressions of several cytokines. Activation of MKK4‐JNK, MEK‐ERK, and MKK3‐p38 signaling pathways, which are associated with cytokine production, was also attenuated by RPE treatment. We hypothesized these RPE‐induced changes are because of its antioxidant activity, because RPE displayed drastic radical scavenging and oxygen radical absorbance capacity (ORAC). Furthermore, high anthocyanins, polyphenols, and flavonoids contents were found in RPE. Hence, these results indicated the skin anti‐inflammatory activity of RPE is because of antioxidant activity.

We hypothesized that hepatic steatosis could be mitigated by the hypolipidemic activity of Schisandra chinensis berry ethanol extract (SCE) via the inhibition of histone acetyltransferase (HAT) activity. HepG2 cells treated with oleic acid (OA) in the presence of SCE exhibited reduced OA-induced lipid accumulation, which was likely mediated by reductions in SREBP-1c expression. SCE attenuated the acetylation of total lysine and H3K9 that was otherwise increased by OA. Male obese mice fed with either a low-fat diet or Western diet exhibited reduced body and liver weights when supplemented with 1% SCE. The SCE-mediated attenuation of hepatic lipid accumulation was accompanied by a decrease in the expression of lipogenic genes. SCE also attenuated the expression of acetylated lysine and non-acetylated forms of H3K9 acetylation in the livers of these mice. Taken together, these results suggest that SCE has potential for further development as a novel therapeutic agent for the prevention of steatosis.

Styrenated phenols are usually synthesized by the reaction of styrene and phenol under acid catalysts. Styrenated phenol involving high content of di-styrenated phenol (DSP) was synthesized, which can be used to prepare styrenated phenol alkoxylate. The solid catalyst used in this study was prepared by impregnation method. SO4 2- on SO4 2-/ZrO2 catalyst was introduced from an aqueous 1M-H2SO4 solution. The catalysts were characterized by SEM images, XRD patterns, and FT-IR spectra. The catalytic activity was examined by measuring the conversion of phenol and styrene in a liquid-phase batch reactor. Almost 100% conversion of both phenol and styrene over 15-SO4 2-/ZrO2 catalyst were obtained at reaction temperature of 100 °C and reaction time of 6 hr. Amount of catalyst to the reactants was 15 wt%. At same reaction conditions, selectivity of MSP, DSP, and TSP were 23.6%, 52.1%, and 5.4%, respectively. It was known that the selectivity to DSP was increased as IR absorption peak of 1236 cm-1 corresponding to O–S–O bonds was increased.

Quercetin is a naturally occurring polyphenol present in various fruits and vegetables. The bioactive properties of quercetin include anti-oxidative, anti-cancer, anti-inflammatory, and anti-diabetic effects. However, the effect of quercetin on skin aging and the direct molecular targets responsible have remained largely unknown. Herein, we investigated the protective effect of quercetin against UV-mediated skin aging and the molecular mechanisms responsible. Treatment with quercetin suppressed UV-induced matrix metalloproteinase-1 (MMP-1) and cyclooxygenase-2 (COX-2) expression and prevented UV-mediated collagen degradation in human skin tissues. Quercetin exerted potent inhibitory effects towards UV-induced activator protein-1 (AP-1) and nuclear factor-kappa B (NF-&kappa, B) activity. Further examination of the upstream signaling pathways revealed that quercetin can attenuate UV-mediated phosphorylation of extracellular signal-regulated kinase (ERK), c-Jun N terminal kinases (JNK), protein kinase B (Akt), and signal transducer and activator of transcription 3 (STAT3). Kinase assays using purified protein demonstrated that quercetin can directly inhibit protein kinase C delta (PKC&delta, ) and Janus kinase 2 (JAK2) kinase activity. Quercetin was observed to bind to PKC&delta, and JAK2 in pull-down assays. These findings suggest that quercetin can directly target PKC&delta, and JAK2 in the skin to elicit protective effects against UV-mediated skin aging and inflammation. Our results highlight the potential use of quercetin as a natural agent for anti-skin aging applications.

Caffeic acid phenethyl ester (CAPE), a naturally occurring bioactive compound, displays anti-inflammatory, anti-carcinogenic, and anti-microbial effects. However, the effect of CAPE on skin photoaging is unknown. Herein, we investigated the inhibitory effect of CAPE against ultraviolet (UV) irradiation-mediated matrix metalloproteinase (MMP)-1 expression and its underlying molecular mechanism. CAPE treatment suppressed UV-induced MMP-1 levels in both human dermal fibroblasts (HDF) and human skin tissues. While CAPE did not display any significant effects against the upstream regulatory pathways of MMP-1, CAPE was capable of reversing UV-mediated epigenetic modifications. CAPE suppressed UV-induced acetyl-histone H3 (Lys9) as well as total lysine acetylation in HDF cells. Similarly, CAPE also attenuated UV-induced lysine acetylations in human skin tissues, suggesting that the CAPE-mediated epigenetic alterations can be recapitulated in ex vivo conditions. CAPE was found to attenuate UV-induced histone acetyltransferase (HAT) activity in HDF. Notably, CAPE was able to directly inhibit the activity of several HATs including p300, CREP-binding protein (CBP), and p300/CBP-associated factor (PCAF), further confirming that CAPE can function as an epigenetic modulator. Thus, our study suggests that CAPE maybe a promising agent for the prevention of skin photoaging via targeting HATs.

Propolis is a resinous substance generated by bees using materials from various plant sources. It has been known to exhibit diverse bioactivities including anti-oxidative, anti-microbial, anti-inflammatory, and anti-cancer effects. However, the direct molecular target of propolis and its therapeutic potential against skin aging in humans is not fully understood. Herein, we investigated the effect of propolis on ultraviolet (UV)-mediated skin aging and its underlying molecular mechanism. Propolis suppressed UV-induced matrix metalloproteinase (MMP)-1 production in human dermal fibroblasts. More importantly, propolis treatment reduced UV-induced MMP-1 expression and blocked collagen degradation in human skin tissues, suggesting that the anti-skin-aging activity of propolis can be recapitulated in clinically relevant conditions. While propolis treatment did not display any noticeable effects against extracellular signal-regulated kinase (ERK), p38, and c-jun N-terminal kinase (JNK) pathways, propolis exerted significant inhibitory activity specifically against phosphorylations of phosphoinositide-dependent protein kinase-1 (PDK1) and protein kinase B (Akt). Kinase assay results demonstrated that propolis can directly suppress phosphoinositide 3-kinase (PI3K) activity, with preferential selectivity towards PI3K with p110&alpha, and p110&delta, catalytic subunits over other kinases. The content of active compounds was quantified, and among the compounds identified from the propolis extract, caffeic acid phenethyl ester, quercetin, and apigenin were shown to attenuate PI3K activity. These results demonstrate that propolis shows anti-skin-aging effects through direct inhibition of PI3K activity.

Objective We examined the potential of tannic acid (TA) as a novel histone acetyltransferase inhibitor (HATi) and demonstrated that TA prevents non-alcoholic fatty liver disease (NAFLD) by inhibiting HAT activity. Methods The anti-HAT activity of TA was examined using HAT activity assays. An in vitro NAFLD model was generated by treating HepG2 cells with oleic and palmitic acids. Male C57BL/6J mice were fed a control diet (CD) or Western diet (WD) with or without supplementation with either 1% or 3% TA (w/w) for 12 weeks. Finally, the possibility of interacting p300 and TA was simulated. Results TA suppressed HAT activity both in vitro and in vivo. Interestingly, TA abrogated occupancy of p300 on the sterol regulatory element in the fatty acid synthase and ATP-citrate lyase promoters, eventually inducing hypoacetylation of H3K9 and H3K36. Furthermore, TA decreased acetylation at lysine residues 9 and 36 of histone H3 protein and that of total proteins. Consequently, TA decreased the mRNA expression of lipogenesis-related genes and attenuated lipid accumulation in vivo. We observed that NAFLD features, including body weight, liver mass, fat mass, and lipid profile in serum, were improved by TA supplementation in vivo. Finally, we demonstrated the possibility that TA directly binds to p300 through docking simulation between ligand and protein. Conclusions Our findings demonstrate that TA, a novel HATi, has potential application for the prevention of NAFLD.

Rh-SP dyad bearing rhodamine (Rh) and spiropyran (SP) moieties was prepared. Reversible photochromic reaction was observed between colorless and nonfluorescent c-Rh-SP and c-Rh-MC with purple color and red fluorescence. Rh-SP can act as a triple chemosensor for Al3+, , and CN −, by absorption and fluorescence spectral changes. The results show colorless solution and orange fluorescence with Al3+, red solution and bright orange fluorescence with , and yellow solution and weak green fluorescence with CN −.

Poly-γ-glutamic acid (PGA) is one of the bioactive compounds found in cheonggukjang, a fast-fermented soybean paste widely utilized in Korean cooking. PGA is reported to have a number of beneficial health effects, and interestingly, it has been identified as a possible anti-cancer compound through its ability to promote apoptosis in cancer cells, although the precise molecular mechanisms remain unclear. Our findings demonstrate that PGA inhibits the pro-proliferative functions of the phorbol ester 12-O-tetradecanoylphorbol-13-acetate (TPA), a known chemical carcinogen in HT-29 human colorectal cancer cells. This inhibition was accompanied by hallmark apoptotic phenotypes, including DNA fragmentation and the cleavage of poly (ADP-ribose) polymerase (PARP) and caspase 3. In addition, PGA treatment reduced the expression of genes known to be overexpressed in colorectal cancer cells, including cyclooxygenase 2 (COX-2) and inducible nitric oxide synthase (iNOS). Lastly, PGA promoted activation of 5' adenosine monophosphate-activated protein (AMPK) in HT-29 cells. Taken together, our results suggest that PGA treatment enhances apoptosis in colorectal cancer cells, in part by modulating the activity of the COX-2 and AMPK signaling pathways. These anti-cancer functions of PGA make it a promising compound for future study.

The reaction of styrene with phenol using photoacid catalyst has been investigated. Upon irradiation with 450 nm light, protonated merocyanine photoacid converts into spiropyran form with releasing proton. The reaction of styrene with phenol has been conducted under irradiation with 450 nm light using merocyanine photoacid catalyst at room temperature in comparison with the results using some selected catalysts including or at the reaction temperature of .

We investigated the anti-cancer effects of beta-sitosterol (BS), a plant-derived sterol in AGS human gastric adenocarcinoma cells and xenograft mouse models. BS significantly reduced cell viability by inducing apoptosis in AGS adenocarcinoma cells. This was accompanied by the formation of apoptotic bodies, as detected by Annexin V, caspase 3/7 activity, and MitoPotential assay. BS stimulated phosphatase and tensin homolog (PTEN) and phospho-AMP-activated protein kinase (p-AMPK) expression. Pharmacological inhibitors or siRNA were used to further analyse the relationship between the two proteins. AMPK was found to represent a likely upstream regulator of PTEN. Additionally, two-dimensional gel electrophoresis was used to identify related proteins in the treatment of BS. The decrease of Hsp90 protein by BS was observed. Induction of PTEN protein and reduction of Hsp90 was mediated by AICAR, an AMPK activator, indicating that AMPK is necessary for PTEN and Hsp90 expression. Additionally, BS was found to be effective through the regulation of cancer biomarker. Furthermore, BS suppressed tumour growth without toxicity in the AGS xenograft mouse models-. Taken together, the present results demonstrate that BS exerts anti-cancer effects in AGS cells and xenograft mouse models by mediating AMPK, PTEN, and Hsp90.

Spiropyran-cored polyamidoamine (PAMAM) dendrons (SP-PAMAMs) were prepared and their solvatochromic and photochromic properties investigated. As with simple merocyanine (MC), MC-PAMAM shows negative solvatochromism. On UV irradiation, colorless SP-PAMAM transforms into colored MC-PAMAM and the reaction occurs a little faster in a more polar solvent. In the dark, MC-PAMAM returns to SP-PAMAM much more slowly in a more polar solvent. On addition of Cu2+, the color of SP-PAMAM solution in acetonitrile changes from colorless to orange, whereas neither color change nor absorption spectral changes are observed with the addition of other metal cations.

Hepatic steatosis is the most common chronic liver disease in Western countries. Both genetic and environmental factors are known as causes of the disease although their underlying mechanisms have not been fully understood. This study investigated the association of DNA methylation with oleic acid-induced hepatic steatosis. It also examined effects of food components on DNA methylation in hepatic steatosis. Genome-wide DNA methylation of oleic acid (OA)-induced lipid accumulation in vitro cell model was investigated using reduced representation bisulfite sequencing. Changes of DNA methylation were also analyzed after treatment with food components decreasing OA-induced lipid accumulation in the model. We identified total 81 regions that were hypermethylated by OA but hypomethylated by food components or vice versa. We determined the expression of seven genes proximally located at the selected differentially methylated regions. Expression levels of WDR27, GNAS, DOK7, MCF2L, PRKG1, and CMYA5 were significantly different between control vs OA and OA vs treatment with food components. We demonstrated that DNA methylation was associated with expression of genes in the model of hepatic steatosis. We also found that food components reversely changed DNA methylation induced by OA and alleviated lipid accumulation. These results suggest that DNA methylation is one of the mechanisms causing the hepatic steatosis and its regulation by food components provides insights that may prevent or alleviate lipid accumulation.

Porphyrin(Por)–spiropyran(SP) hybrid compounds, including Por–SP dyad, Por–SP2 triad, and Por–SP4 pentad, were prepared and characterized by 1H NMR, MALDI-TOF MS and UV–Vis spectroscopies. Upon 350 nm UV irradiation of Por–SPn (n = 1, 2, 4) in dichloromethane, unusual red-shifted absorption spectra were observed with the colour change from pink into green. Probably due to the protonation of core nitrogens in porphyrin ring, their absorption maxima in dichloromethane were shifted from 418 (Soret band), 515, 550, 590, 645 (four Q bands) nm into 450 and 665 nm. Also, fluorescence maxima were also shifted from 650 and 715 nm to 692 nm. In the other hands, upon irradiation with 350 nm UV light in THF, the colour changed from pink into violet and absorption band at 590 nm increased and the fluorescence spectra showed the decrease of 650 and 715 nm bands and increase of 600–640 nm band, due to the normal ring-opening reaction of spiropyran moiety into merocyanine. In the dark, original absorption and fluorescence spectra were recovered very slowly in dichloromethane, but quickly in THF. The reversible photochromic reactions of Por–SPn (n = 1, 2, 4) in dichloromethane and THF were investigated by observing absorption and fluorescence spectral changes during UV irradiation or standing in the dark.

In this study, we performed in vitro and in vivo studies to examine whether a 70% ethanol extract of Prunus mume fruits (EMS) exhibits anti-diabetic effects. Treatment with EMS increased glucose uptake in C2C12 myotubes, and also increased PPAR-γ activity or PPAR-γ mRNA expression. To confirm these in vitro results, we next conducted an animal experiment. A high-fat diet significantly increased the body weight, fat accumulation, and glucose levels in mice. Under the same conditions, 5% EMS attenuated the high-fat diet-induced increase in body weight and fat accumulation and improved the impaired fasting glucose level and glucose tolerance. High performance liquid chromatography analysis demonstrated that EMS contained chlorogenic acid, caffeic acid, rutin, luteolin-7-glucoside, naringin, apigenin-7-glucoside, and hesperidin. Taken together, these findings suggest that EMS exerts an anti-diabetic effect both in vitro and in vivo, which is mediated, at least in part, by the activation of PPAR-γ.

E-mail: ejs@sunchon.ac.krReceived July 5, 2013, Accepted July 17, 2013Key Words : Porphyrin, Diprotonated porphyrin, Spiropyran, Merocyanine, AggregationPorphyrin (Por) has a strong absorption characteristics inthe range of sunlight due to a chemical structure of highconjugation and rigidity, good redox properties, and well-established synthetic methods. Accordingly, porphyrin-basedmulticomponent compounds have been investigated in avariety of applications such as artificial light-harvestingantenna, molecular energy storage devices, solar cells, opto-electronic switches, and photodynamic therapy.

We conducted the airborne magnetic and radiometric survey for the characterization of the black shale related and pyrometamorphic uranium deposits distributed in Geumsan area. For the successful characterization of the uranium deposits, the general geological and structural geological features were investigated based on the lithological and linear feature analysis to individual magnetic and radiometric data as the first step. Lithological analysis from the magnetic reduction to the pole and downward continuation map revealed that prominent positive anomalies caused by black and dark gray slate member were clearly recognized as magnetic sources. These results indicate that magnetic survey, even though it is not a direct method for the detection of uranium, can be a useful tool in uranium detection. By the linear feature analysis based on 2nd vertical derivative and curvature map, two linearments corresponded the gray hornfels and black slate member were extracted and in succession, the additional uranium potential zone was inferred. Final discrimination whether uranium-rich or not was confirmed by radiometric and uranium anomaly map. From these analysis, we finally concluded that uranium deposit originated by pyrometamorphic process was confined near the intrusive area only. On the contrary, it was found that black shale related uranium deposit is distributed and extended through out the entire survey area with south-west to north-east direction. In addition, from the linear feature analysis based on radiometric total anomaly map, the typical discontinuous characteristics were recognized in areas where uranium-contained linearments cross the faults. From the above discussion, we concluded that airborne magnetic and radiometric survey are complementary to each other. So it is preferable to carry out simultaneously for the efficient data processing and fruitful interpretation.

We previously showed that gintonin, an exogenous lysophosphatidic acid (LPA) receptor ligand, attenuated β-amyloid plaque formation in the cortex and hippocampus, and restored β-amyloid-induced memory dysfunction. Both endogenous LPA and LPA receptors play a key role in embryonic brain development. However, little is known about whether gintonin can induce hippocampal cell proliferation in adult wild-type mice and an APPswe/PSEN-1 double Tg mouse model of Alzheimer's disease (AD). In the present study, we examined the effects of gintonin on the proliferation of hippocampal neural progenitor cells (NPCs) in vitro and its effects on the hippocampal cell proliferation in wild-type mice and a transgenic AD mouse model. Gintonin treatment increased 5-bromo-2'-deoxyuridine (BrdU) incorporation in hippocampal NPCs in a dose- and time-dependent manner. Gintonin (0.3 μg/ml) increased the immunostaining of glial fibrillary acidic protein, NeuN, and LPA1 receptor in hippocampal NPCs. However, the gintonin-induced increase in BrdU incorporation and immunostaining of biomarkers was blocked by an LPA1/3 receptor antagonist and Ca2+ chelator. Oral administration of the gintonin-enriched fraction (50 and 100 mg/kg) increased hippocampal BrdU incorporation and LPA1/3 receptor expression in adult wild-type and transgenic AD mice. The present study showed that gintonin could increase the number of hippocampal neurons in adult wild-type mice and a transgenic AD mouse model. Our results indicate that gintonin-mediated hippocampal cell proliferation contributes to the gintonin-mediated restorative effect against β-amyloid-induced hippocampal dysfunction. These results support the use of gintonin for the prevention or treatment of neurodegenerative diseases such as AD via promotion of hippocampal neurogenesis.

Ketosteroid isomerase (3-oxosteroid Δ(5)-Δ(4)-isomerase, KSI) from Pseudomonas putida catalyzes allylic rearrangement of the 5,6-double bond of Δ(5)-3-ketosteroid to 4,5-position by stereospecific intramolecular transfer of a proton. The active site of KSI is formed by several hydrophobic residues and three catalytic residues (Tyr14, Asp38, and Asp99). In this study, we investigated the role of a hydrophobic Met112 residue near the active site in the catalysis, steroid binding, and stability of KSI. Replacing Met112 with alanine (yields M112A) or leucine (M112L) decreased the kcat by 20- and 4-fold, respectively. Compared with the wild type (WT), M112A and M112L KSIs showed increased KD values for equilenin, an intermediate analogue; these changes suggest that loss of packing at position 112 might lead to unfavorable steroid binding, thereby resulting in decreased catalytic activity. Furthermore, M112A and M112L mutations reduced melting temperature (Tm) by 6.4°C and 2.5°C, respectively. These changes suggest that favorable packing in the core is important for the maintenance of stability in KSI. The M112K mutation decreased kcat by 2000-fold, compared with the WT. In M112K KSI structure, a new salt bridge was formed between Asp38 and Lys112. This bridge could change the electrostatic potential of Asp38, and thereby contribute to the decreased catalytic activity. The M112K mutation also decreased the stability by reducing Tm by 4.1°C. Our data suggest that the Met112 residue may contribute to the catalytic activity and stability of KSI by providing favorable hydrophobic environments and compact packing in the catalytic core.

This article presents that deicers such as calcium chloride (CaCl2) and EFDs (Eco-Friendly Deicers) composed with organic acids affect germination of seeds buried in old-field soil. CaCl2, one of a commonly used deicer in the world, have shown an inhibitory effect on the germination of the buried seeds. Species richness, species diversity, and total biomass of the plant community after germinating were greatly decreased with increase of CaCl2 concentration. The germination of buried seeds was inhibited seriously by CaCl2, but the degree of its varied significantly with plant species. EFD1 manufactured from organic chemicals showed the higher inhibition on germination than CaCl2. However, EFD2 composed with organic acids of food waste didn’t have an inhibitory effect on the species richness after germination and rather enhanced the germination and initial growth of the seedlings. The positive effect was evaluated that EFD2 caused to supply nutrition on germination or growth of buried seeds. The deicers may change dynamically the plant community of the roadside because the response of germination and growth by deicers differ from plant species.

The porphyrin-incorporated arylether dendrimers ZnP-D1 and ZnP-D4 were investigated to discover the influence of dendritic environments for the axial ligation of pyridine and photoinduced electron transfer by methyl viologen. Absorption and fluorescence spectra of ZnP, ZnP-D1, and ZnP-D4 were measured in dichloromethane with the addition of pyridine or methyl viologen dichloride. Axial ligation of pyridine was confirmed by red-shifted absorption spectrum. The complex formation constants Kf (Table 1) for axial coordination of pyridine on ZnP, ZnP-D1, and ZnP-D4 were estimated to be 4.4 × 10 3 M �1 , 3.3 × 10 3 M �1 , and 1.7 × 10 3 M �1 , respectively. The photoinduced electron transfer to methyl viologen dichloride was confirmed by fluorescence quenching. Stern-Volmer constants Ksv for ZnP, ZnP-D1, and ZnP-D4 were calculated to be 2.6 × 10 3 , 2.5 × 10 3 , and 2.1 × 10 3 , respectively. ZnP-D4 surrounded by 4 aryl ether dendrons shows the smallest Kf and Ksv values, with comparison to ZnP and ZnP-D1.

Zinc porphyrin, Azacrown ether, Cation recognition, Axial coordinationIt is very interesting that the presence or absence of hydrogen atoms can remarkably influence operation of molecular systems as well as natural systems. Induction of structural changes of natural receptors through the variations in the pH of the environ-ment is one of the most versatile methods to regulate the activity by enhancing or diminishing the receptor’s binding efficacy.

Benzyl arylether dendrimers with zinc porphyrin core and terminal vinyl groups have been synthesized and their photophysical properties and the influence of dendritic environments were investigated. Free base porphyrin-cored benzyl arylether dendrimers 1a-1c and 3a-3c, and their zinc derivatives 2a-2c and 4a-4c have been prepared. Absorption spectra are similar for all porphyrin-cored benzyl arylether dendrimers, except that absorption intensity at 280 nm increases in the higher generation of dendrimer. Fluorescence spectra are similar with two bands for all free base porphyrin dendrimers 1a-1c and 3a-3c, although fluorescence intensity ratio of shorter wavelength emission band to longer wavelength band varies with the generation of dendrimer. Emission efficiencies of 1a-1c and 3a-3c are lower than that of TTP. Emission efficiencies of 2a-2c and 4a-4c are higher than that of ZnTTP. Absorption and emission properties of 1a-1c, 2a-2c, 3a-3c, and 4a-4c were affected negligibly with dendritic environments.

Azobenzene, Isomerization, Au nanoparticle, Organic-inorganic nanohybrid, Absorption spectraRecently, inorganic nanoparticles have attracted greatattention because nanoparticles exhibit interesting size-dependent physical and chemical properties due to inter-mediate size between single molecules and bulk materials.

Azobenzene-cored dendrons having the photoisomerizable azobenzene core and terminal vinyl groups have been prepared. Absorption bands of azobenzene-cored dendrons are similar except more intense 280 nm band in higher generation azobenzene dendron. All three azobenzene-cored dendrons show reversible photoisomerization similar to simple azobenzene, irrespective of the generation of dendron. On 350 nm irradiation, absorption band around 344 nm decreases and 436 nm band increases. Photoisomerization reactions are very fast for all three azobenzene-cored dendron and the reaction efficiency is dependent of its generation and solvent. In the dark, slow thermal reversion to original absorption spectrum is observed.

Makgeolli is a traditional wine in Korea and has been traditionally believed to exhibit health benefits. However, the inhibitory effect of dealcoholized makgeolli (MK) on cancer has never been investigated scientifically. In this study, MK exhibited an anti-angiogenic effect by inhibiting tube formation in human umbilical vein endothelial cells, without cytotoxicity. Treatment with MK reduced the proliferation of AGS human gastric adenocarcinoma cells in a dose-dependent manner and increased the sub-G1 population. Next, we evaluated whether MK could induce apoptosis in AGS cells by using the terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) assay or Annexin V method. Treatment with MK at 500 and 1,000 μg/ml increased the number of TUNEL-positive AGS cells. Under the same conditions, MK-treated (500 and 1,000 μg/ml) cells showed significant induction of early or late apoptosis, compared with untreated cells (no induction). In addition, MK also induced phosphatase and tensin homolog (PTEN) expression in AGS cells. However, p53 expression in AGS cells was not changed by MK treatment. Furthermore, MK at 500 mg/kg·d reduced the tumor size and volume in AGS tumor xenografts. Taken together, MK may be useful for the prevention of cancer cell growth.

and other molecular electronicand photonic devices, because of their attractive electronicand redox properties and with the ease of modification bythe development of various synthetic routes. The fact thatthere are many sites on the porphyrin at which to attachelectron-releasing or electron-withdrawing groups suggeststhat tremendous electronic modulation of the porphyrinshould be possible.

Four 1-(9-anthryl)-2-heteroarylethene derivatives containing sulfur or oxygen atom such as 1-(9-anthryl)-2-(2-thiophenyl)ethene (ATE), 1-(9-anthryl)-2-(2-benzo[ b ]thiophenyl)ethene (ABTE), 1-(9-anthryl)-2-(2-furanyl)ethene (AFE), and 1-(9-anthryl)-2-(2-benzofuranyl)ethene (ABFE) have been prepared and their excited state properties have been investigated in cyclohexane, acetonitrile, and methanol. These sulfur- or oxygen-heteroaromatic ring derivatives show solvent-dependent fluorescence and photoisomerization behavior, due to the intramolecular charge-transfer character of the lowest S 1 state. Substituent effect on fluorescence and photoisomerization of ATE further supports the contribution of the intramolecular charge-transfer character to the lowest S 1 state, which is more increased by the introduction of electron-withdrawing substituent into anthracene ring.

The preparation and photophysics of organometallic Ir(III) complexes with 3-phenylpyridazine (H6Clppdz) and its derivative are reported. IrCl 3 · n H 2 O reacts with H6Clppdz, and 3-chloro-6-(3 ′ -methoxyphenyl)-4-methyl-pyridazine (MCOMppdz) to give the corresponding chloride-bridged dimers, (6Clppdz) 2 Ir( μ -Cl) 2 Ir(6Clppdz) 2 and (MCOMppdz) 2 Ir( μ -Cl) 2 Ir(MCOMppdz) 2 in good yields. These chloride-bridged dimers are cleaved with 2-pyrazinecarboxylic acid (Hpyzc), 2-picolinic acid (Hpic), acetylacetone (Hacac), and 2,2,6,6-tetramethyl-3,5-heptanedione (Htmd) to give the corresponding monomer, (6Clppdz) 2 Ir(pyzc), (6Clppdz) 2 Ir(pic), (6Clppdz) 2 Ir(acac), (6Clppdz) 2 Ir(tmd), (MCOMppdz) 2 Ir(acac), and (MCOMppdz) 2 Ir(tmd), respectively. The complexes show bright orange to red luminescence at room temperature and the emission wavelenghts are affected by the ancillary ligands as well as cyclometalating ligands (593–664 nm).

It is interesting to introduce viologen moiety into photoactive compounds such as porphyrin and anthracene in the study of supramolecular system such as pseudorotaxanes. For the construction of photoactive pseudorotaxane based on porphyrin-viologen-anthracene triad or its zinc derivative threaded with bis-p-phenylene-34-crown-10 macrocycle, porphyrin-viologen-anthracene triad 1 and its zinc derivative zinc porphyrin-viologen-anthracene triad 2 were prepared and their absorption and fluorescence spectral properties were measured.

Noncovalently linked electron donor-acceptor dyad consisting of zinc tetratolylporphyrin and pyridine-appended ruthenium trisbipyridine complex was prepared, via axial coordination of pyridine moiety in ruthenium trisbipyridine complex on zinc tetratolylporphyrin. For the purpose of comparison, axial coordination of pyridine-appended 2,2'-bipyridine on zinc tetratolylporphyrin was also investigated. The K values were determined based on absorption or fluorescence studies. The fluorescence of zinc tetratolylporphyrin was efficiently quenched upon axial coordination of pyridine moiety, probably due to the photoinduced electron transfer from zinc tetratolylporphyrin to ruthenium trisbipyridine, supported by free energy estimation.

Background/objectives Non-alcoholic fatty liver disease (NAFLD) is a leading cause of chronic liver disease and is closely associated with metabolic syndrome. In the present study, we observed the effect of ethanol extract of Allium fistulosum (EAF) on NAFLD and have suggested the possibility of using EAF as a natural product for application in the development of a treatment for NAFLD. Materials/methods The preventive effect on hepatic lipid accumulation was estimated by using an oleic acid (OA)-induced NAFLD model in vitro and a Western diet (high-fat high-sucrose; WD)-induced obese mouse model. Animals were divided into three groups (n = 7): normal diet group (ND), WD group, and WD plus 1% EAF group. Results EAF reduced OA-stimulated lipid accumulation in HepG2 cells in the absence of cellular cytotoxicity and significantly blocked transcriptional activation of sterol regulatory element-binding protein 1 and fatty acid synthase genes. Subsequently, we investigated these effects in vivo in mice fed either ND or WD in the presence or absence of EAF supplementation. In comparison to the ND controls, the WD-fed mice exhibited increases in body weight, liver weight, epididymal fat weight, and accumulation of fat in hepatocytes, and these effects were significantly attenuated by EAF supplementation. Conclusions Allium fistulosum attenuates the development of NAFLD, and EAF elicits anti-lipogenic activity in liver. Therefore, EAF represents a promising candidate for use in the development of novel therapeutic drugs or drug combinations for the prevention and treatment of NAFLD.

in the last ten years because oftheir thermal and optical stability and fatigue resistance. Wereport here the preparation of trans-1-(9-anthryl)-2-(2-thienyl)ethene (t-AThE), a thiophene derivative of trans-1-(9-anthryl)-2-phenylethene (t-APE), and its absorption andfluorescence spectral data and photoisomerization behavior. While stilbene shows very weak fluorescence due to veryefficient two-way photoisomerization

The fluorescence and photoisomerization quantum yields of trans-1-(9-anthryl)-2-(4-pyridyl)ethene ( t-4APyE), 1-(10-methyl-9-anthryl)-2-(4-pyridyl)ethene (t-4-MeAPyE), and 1-(10-chloro-9-anthryl)-2-(4pyridyl)ethene (t-4-ClAPyE) were measured in cyclohexane, acetonitrile, and methanol at room temperature. Polar solvents result in the drastic reduction of fluorescence quantum yield and increase of photoisomerization quantum yield for all three compounds. These results are probably due to the stabilization of intramolecular charge transfer (ICT) excited state in polar solvent. The higher contribution of ICT in the presence of more electron-donating methyl substituent, manifested by largest positive fluorescence solvatochromism, indicates that the pyridine ring acts as an electron acceptor. Protonation or methylation makes pyridine ring stronger electron acceptor and causes long-wavelength ground state charge transfer absorption band and complete quenching of fluorescence. The fluorescence from t-4-APyE derivatives can be switched off responding external stimuli viz. medium polarity, protonation, or methylation.

The photophysical properties of the lowest singlet and triplet excited states of some trans-1-(9-anthryl)-2-(n-naphthyl)ethenes (n = 1 or 2, t-n-ANE) and trans-1-(9-anthryl)-2-(n-quinolyl)ethenes (n = 2–4, t-n-AQE) derivatives have been studied in methylcyclohexane and acetonitrile at room temperature. The hydrocarbon derivative t-1-ANE exhibits fluorescence and intersystem crossing quantum yields (which are independent of solvent polarity) very similar to those of trans-1-(9-anthryl)-2-phenylethene. For the monoaza analog t-4-AQE, the fluorescence and triplet quantum yields in acetonitrile are much lower than in methylcyclohexane. t-4-AQE undergoes trans → cis photoisomerization even in the nonpolar solvent. t-2-ANE and t-3-AQE show remarkably high fluorescence efficiency. Surprisingly, the excited state properties of t-2-AQE are highly solvent-dependent. In polar solvents, the fluorescence quantum yield is reduced, while the photoisomerization yield increases. But, for both t-2- and t-4-AQE, the triplet quantum yield also decreases with solvent polarity. Therefore, photoisomerization probably proceeds via a singlet manifold. The singlet oxygen quantum yields of t-n-AQE and t-n-ANE are strongly dependent on both the solvent polarity and oxygen concentration, indicating that singlet oxygen is very likely being generated from both the excited singlet and triplet states.

The fluorescence quenching of various substituted tetraphenylporphyrins and their zinc complexes by ruthenium(II) tris(2,2′-bipyridine) has been investigated in dichloromethane. While fluorescence quenching was not effective for free base porphyrins, but in the case of zinc porphyrins fairly efficient. Plots for the Stern–Volmer quenching constant versus the calculated free energy change (Δ G red ) for photoinduced oxidative electron transfer (ET) processes from the excited singlet porphyrins to ruthenium(II) tris(2,2′-bipyridine) were shown to be linear. Among porphyrins/ruthenium(II) tris(2,2′-bipyridine) pairs examined in this study, ZnTMeOPP/ruthenium(II) tris(2,2′-bipyridine) pair exhibited most efficient fluorescence quenching as predicted to carry out most favorable photoinduced oxidative electron transfer processes by the calculated free energy changes (Δ G red ).

The fluorescence properties and photoisomerization behavior for trans and cis isomers of 1-(9-anthryl)-2-(2-pyrazinyl)ethene (APzE). a diaza analogue of 1-(9-anthryl)-2-phenylethene (9-APE), were studied. The fluorescence maximum (λ 1 ). quantum yield ( Φ t ) and lifetime ( τ t ) of t -APZE were solvent-dependent reflecting the intramolecular charge transfer character in the lowest excited singlet state. However, in polar protic solvent, some discrepancy was observed probably due to protonation on the nitrogen atoms. The photoisomerization of t -APzE was observed even in very nonpolar solvent, in contrast that the parent t -9-APE did not photoisomerize in any solvent and photoisomerization of monoaza analogues t 1-(9-anthryl)-2-( n -pyridyl)ethenes ( n -APyE) was very inefficient in nonpolar solvent. The quantum yield of the trans → cis photoisomerization ( Φ t → c ) of t -APzE was also solvent-dependent. Not only the inverse dependence for Φ f -and Φ t → c , of t -APzE on the temperature and the solvent polarity but also hiacetyl-sensitized photoisomerization experiment indicate that the photoisomerization of t -APzE occurs, at least in part, via the excited singlet state. In air-saturated solution, another side photoproduct was observed in all solvent examined and identified as anthraquinone, a photo-oxidation product. For c -APzE, the τ t , is too short to measure and Φ t , is relatively low. Quantum yields of fluorescence and cis→trans photoisomerization of c -APzE in various solvent and temperature indicate singlet mechanism for the cis → trans photoisomerization of c -APzE in polar solvent but mixed singlet/triplet mechanism in nonpolar solvent. On irradiation of c -APzE, the photo-oxidation product was not generated at all in any solvent. In n -hexane, photocyclization competing with photoisomerization was observed both for t - and c -APzE.

Recently, the development of chemosensor associated with fluoroionophore has attracted great attention. Fluoroionophore is a compound combining the ionophore and fluorophore, where ionophore binds selectively with a specific ion and fluorophore generates a fluorescence signal upon ion binding. Depending on the nature of fluorophore-ionophore interaction in fluoroionophore, fluorescence properties of fluorophore such as fluorescence intensity or fluorescence wavelength maximum may be influenced by ion capture of ionophore. Sensitivity of fluorophore may be associated with the ionic recognition ability of the ionophore, if the fluorophore may be perturbed by the coordination of cation. The recent increase of interest in the synthesis of crown ether derivatives incorporating different fluoroionophores is recently due to their application as alkali metal ion sensors in biochemical analysis and medical diagnostics. In particular, azacrown ether, a typical ionophore, acts as an electron-rich donor as well as a ligand of the cation. The electron pair on the nitrogen heteroatom in electron-rich azacrown ether could be transferred towards electron deficient fluorophore in a π-conjugated D-A arrangement, through the charge transfer interaction between ionophore, an electron donor, and fluorophore, an electron acceptor. The efficient intramolecular charge transfer takes part in the modification of the first electronic transition state of the fluorophore and may lead to weaken the fluorescence from fluorophore. Upon binding of a cation into ionophore cavity, the electron pair on nitrogen heteroatom of ionophore is stabilized and the intramolecular charge transfer is inhibited. Therefore, the original electronic configuration of the unsubstituted fluorophore is recovered, so that fluorescence may be strengthened. Many fluoroionophores including stilbenyl-, aryl-, or styryl-crown ether derivatives containing a stilbene, styrene or aryl moiety as a fluorophore and a crown ether/azacrown ether moiety as an ionophore have been investigated. However, the main disadvantage of these fluoroionophore is the relatively small changes in fluorescence intensity upon cation binding. Incorporation of more efficient fluorophore such as anthracene into fluoroionophore may lead to more remarkable change of fluorescence signal depending on the cation binding. Recent work has concerned the binding of various fluorophores to the N-phenylaza-15-crown-5 and their spectroscopic and complexation properties. This paper concerns the synthesis of N-phenylaza-15-crown-5 derivative containing anthrylethene chromophore and the effect of the complexation with various alkali metal cations on the absorption and fluorescence behavior. We prepared N-[4-(2-anthracen-9-yl-vinyl)-phenyl]-aza15-crown-5 (1), a azacrown ether derivative containing 1-(9anthryl)-2-phenylethene (9-APE) moiety, by Wittig coupling between N-[4-formyl-phenyl]-aza-15-crown-5 and 9bromomethylanthracene. It is known that t-9-APE, a styrene derivative containing highly fluorescent anthracene, shows fairly strong fluorescence (Φf = 0.45, λf = 476 nm in acetonitrile), coming from the locally excited state which the excitation energy is localized on anthracene ring. For 1-(9-anthryl)-2-(4-methoxyphenyl)ethene (MeO-APE) containing an electron donating substituent methoxy group, fluorescence becomes weak and is red-shifted (Φf = 0.028, λf = 494 nm in acetonitrile) due to the contribution of the intramolecular