The rates of the aminolysis of S-phenyl substituted-acetate series $(RC(=O)SC_6H_4Z$, with R=Me, Et, i-Pr, t-Bu and Bn) with benzylamines $(XC_6H_4CH_2NH_2)$ are not correlated simply with the Taft's polar $({\sigma}^{\ast})$ and/or steric effect constants $(E_s)$ of the substituents due to abnormally enhanced rate of the substrate with R=Et. Furthermore, the cross-interaction constant, ${\rho}x_z$ , is the largest with R=Et. These anomalous behaviors can only be explained by invoking the vicinal bond $({\sigma})$-antibond $({\sigma}^{\ast})$ charge transfer interaction between C-$C{\alpha}$ and C-S bonds. In the tetrahedral zwitterionic intermediate, $T^{\pm}$ , formed with R=Et the vicinal ${\sigma}_{c-c}-{\sigma}^{\ast}_{c-s}$ delocalization is the strongest with an optimum antiperiplanar arrangement and a narrow energy gap, ${\Delta}{\varepsilon}={\varepsilon}_{{\sigma}^{\ast}}-{\varepsilon}_{\sigma}$. Due to this charge transfer interaction, the stability of the intermediate increases (with the concomitant increase in the equilibrium constant K (= $k_a/k_{-a}$)) and also the leaving ability of the thiophenolate leaving group increases (and hence $k_b$ increases) so that the overall rate, $k_n\;=\;Kk_b$, is strongly enhanced. Theoretical support is provided by the natural bond orbital (NBO) analyses at the B3LYP/6-31+$G^{\ast}$ level. The anomaly exhibited by R=Et attests to the stepwise reaction mechanism in which the leaving group departure is rate limiting.
In this study, the colorimetric sensor, polyester (PET) fabric dyed with lead (II) acetate (Pb(C2H3O2)2), was fabricated and characterized for the detection of the hydrogen sulfide (H2S). The surface morphology of the fabric was determined using scanning electron microscope and energy-dispersive X-ray spectroscopy. The optical properties of the fabric were evaluated by measuring the variation in the blue value of an RGB sensor. The fabric showed a significant color change, high linearity (R2 : 0.98256), and fast response time (< 1.0 s) when exposed to H2S. This is because the sensor is highly porous and permeable to the gas. The fabric can not only be used as a hydrogen sulfide sensor but also be used to detect and prevent H2S influx using sticky tape on pipelines.
This studies were performed to develop a Korean traditional folk liquor namely Gangha-ju has been prepared at Bosung district in Korea, and manufacturing conditions and anti-oxidation activity and anti-microbial activity of Gangha-ju were investigated. Ethyl-alcohol 20% and 30% Gangha-ju were brewed with glutinous rice wine, distilled liquor and 6 herbs of ginger, cinnamon, etc. Chemical and physical properties of 30% Gangha-ju were acidity 0.22, pH 4.31, amino acidity 3.26, transmittance 59 and conductivity $911\;{\mu}s/m$, and 20% Gangha-ju were 0.43, 4.20, 6.26, 62 and $924\;{\mu}s/m$. Volatile flavor compounds of ethyl alcohol, acetic acid, butanol, n-amyl alcohol, iso-pentyl alcohol, ethyl acetate, butyl acetate, acetaldehyde and furfural were detected, and main aroma compounds of Gangha-ju were isopentyl alcohol and ethyl acetate. Anti-oxidation activity by DPPH method was evaluated 31.32%, and nitrite scavenging effect was 31.79%. Anti-microbial activity against several microorganisms was pronounced strong activity over a wide range of test organisms, and Leuconostoc mesenteroids and Salmonella Ttyphimurium, Staphylococcus epidermidis were found to be more sensitive to Gangha-ju than Escherichia coli and Aspergillus flavus.
2-Thiouracil-5-sulphonic acid N-(4-acetylphenyl) Amide (1) was reacted with a series of aromatic aldehydes giving chalcones 2 (Claisen-Schemidt reaction), some of these chalcones were reacted with urea and thiourea giving pyrimidine-2-one and pyrimidine-2 thione derivatives respectively of the type 3a,b and 4a,b. In addition many chalcones were reacted with hydroxylamine hydrochloride giving isoxazoline derivatives 5a,b. They could also reacted with phenylhydrazine to give pyrazoline derivatives 5a,b, chalcones also were reacted withethylcyano acetate and/or malononitryl in pyridine giving pyran derivatives 7a,c and 8a,c. In another pathway chalcones were epoxidised by $H_{2}O_{2}$ giving epoxides 9a,c which in turn were reacted with phenylhydrazine giving 4-hydroxypyrazoline derivatives 10a,c. In another reaction chalcones were reacted with ethylcyanoacetate in presence of amm.acetate giving pyridone derivatives 11a,d which could be prepared also in exellent yield from compound 1 by its reaction with certain aromatic aldehydes and ethylcyanoacetate in presence of ammonium acetate. Finally, compound 1 was reacted with semicarbazide giving semicarbazone intermediate 12 which in turn was reacted with thionyl chloride giving thiadiazole derivative 13. The biological effects of some of the new synthesized compounds were also investigated.
Lee, S.C.;Lee, H.J.;Kim, D.W.;Park, J.G.;Han, In K.
Asian-Australasian Journal of Animal Sciences
/
v.13
no.3
/
pp.300-306
/
2000
This experiment was carried out to determine the contributions of acetate, glucose, amino acids and amino acid metabolites as carbon precursors for the incorporation of radioisotope, in intramuscular and subcutaneous adipose tissue and the effects of insulin on lipogenesis and adrenergic agent, norepinephrine on lipolysis in both tissues. The rate of incorporation of $C^{14}$ labelled acetate, glucose, leucine, isoleucine and ${\alpha}$-ketoisocaproic acid into adipose tissue has been measured in subcutaneous and intramuscular adipose tissues. The rate of incorporation was greater (p<0.05) from acetate than glucose in both subcutaneous and intramuscular adipose tissue and the rate of incorporation of carbon precursors into adipose tissues was greater in subcutaneous than in intramuscular adipose tissues. In comparison of amino acids, the rate was highest (p<0.05) with leucine followed by isoleucine and ${\alpha}$-ketoisocaproic acid in subcutaneous adipose tissue, in which there were no differences. Also, in intramuscular tissue, leucine was highest (p<0.05), and the rate of incorporation decreased in the same order. The rates of carbon precursor incorporation appeared to be higher in subcutaneous than in intramuscular tissue. For incorporation of radio-labelled acetate and glucose into intramuscular adipose tissue. preincubated for 48 hrs with insulin and IGF-1, insulin was the most effective to stimulate the incorporation of precursors in both substrates but there was no difference between insulin and IGF-1 in glucose incorporation. For glyceride-fatty acid synthesis, acetate was significantly (p<0.05) greater than glucose in both subcutaneous and intramuscular adipose tissue, and glyceride-glycerol synthesis was greater (p<0.05) for glucose than acetate in both adipose tissues. The rates of lipogenesis from both precursors were slightly greater in subcutaneous than intramuscular adipose tissue. There was significant (p<0.05) site effect in insulin treatment for glyceride-fatty acid synthesis. But there were no significance in control and norepinephrine. For glyceride-glycerol synthesis, there was no site effect caused by hormonal treatment. Insulin was the most effective (p<0.05) in glyceride fatty acid synthesis, while norepinephrine was the same as control. Compared with control, glyceride-glycerol synthesis from acetate in insulin treatment was significantly (p<0.05) low in subcutaneous, but high in intramuscular tissue. At the same time, in both tissues, it was lower in norepinephrine treatment than in control. Glyceride-glycerol synthesis from glucose was highest (p<0.05) in norepinephrine treatment followed by insulin although there was no significance between insulin and control. Lipolysis was not affected by insulin but was increased by norepinephrine when added to adipose tissue incubations in vitro. Rates of basal lipolysis were greater in subcutaneous adipose tissue than in intramuscular adipose tissue.
Kwanok, Fujisaka #5, Paldal, and Suwon #82 as japonica type and IR-262 and CP-slo as indica type of rice seeds were selected for this experiment among varieties grown in Korea. Activities of crude enzymes extracted from germinating seeds of these varieties on malathion and p-nitrophenyl acetate as substrates, esterase zymograms with 1-naphthyl acetate as substrate, and some observations are summarized as follows: 1. Activities per unit volume of crude enzyme preparations on malathion were in the order of Kwanok>IR-262>Fujisaka #5>CP-slo>Paldal>Suwon #82. 2. Esterase zymograms on agar-gel electrophoretograms exhibited three to four bands two electrodes with little difference among varieties, nevertheless showing a wide and strongly-colored band toward cathode. Suwon #82 has a somewhat different pattern from others. 3. Enzyme activities per milligram protein with p-nitrophenyl acetate as substrate were in the order of CP-slo>IR-262>Paldal>Kwanok>Suwon #82>Fujisaka #5, indicating that activities of indica type are much stronger than those of japonica type, but not in agreement with results with malathion. 4. Malathion did not much inhibit the esterase activity at the concentration of 0.2PPM on electrophoretograms. 5. It is supposed that there is a complex esterase system hydrolyzing malathion and p-nitrophenyl acetate in germinating rice seeds.
The Journal of Korean Medicine Ophthalmology and Otolaryngology and Dermatology
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v.20
no.1
s.32
/
pp.115-129
/
2007
Objectives : This study was carried out to evaluate anti-oxidative, anti-microbial and anti-cancer effect for clinical application of Bibangtalmyungsan (BTS) Results : 1. The oxidative effects were measured by polyphenol, DPPH radical scavenging activity. BTS water extract was showed more effective than ethanol extract and also various solvent fractions from BTS water extract showed effective in the following order : ethyl acetate fraction > butanol fraction > hexane fraction ${\fallingdotseq}$ chloroform fraction ${\fallingdotseq}$ aqueous fraction 2. The results of anti-microbial effects were as follows. 1) Antibacterial activities of BTS extracts against Gram's negative and positive bacteria were ineffective 2) Antifungal activities of the BTS extracts against Aspergillus spp. , Trichohyton mentagrophyte KTCC 1077 were not effective. 3. The result of anti-cancer effects were as followings: 1) BTS ethanol extract was more effective than water extract against Caco-2, Calu-6, but it had cytotoxic effect against NIH3T3. 2) On the Caco-2, effective only in ethyl acetate $fraction(IC_{50}:$ 35.81 ${\mu}g/ml)$. 3) On the Calu-6, the most effective in ethyl acetate $fraction(IC_{50}:$ 189.65 ${\mu}g/ml)$ and effective In butanol $fraction(IC_{50}:$ 299.74 ${\mu}g/ml)$ and hexane $fraction(IC_{50}:$ 345.13 ${\mu}g/ml)$ 4) On the SUN-601, $IC_{50}$ value was within 80 ${\mu}g/ml$ in ethyl acetate fraction and hexane fraction. 5) On the HCT-1l6, the most effective in ethyl acetate $fraction(IC_{50}:$ 82.94 ${\mu}g/ml)$ and effective in hexane $fraction(IC_{50}:$ 374.56 ${\mu}g/ml)$. 6) On the AML-2/WT, the most effective in ethyl acetate $fraction(IC_{50}:$ 41.44 ${\mu}g/ml)$ and effective In hexane $fraction(IC_{50}:$ 303.01 ${\mu}g/ml)$. 7) On the NIH3T3, effective only in ethyl acetate $fraction(IC_{50}:$ 203.42 ${\mu}g/ml)$, but it was more ineffective than other cancer cells. Conclusion : These result suggest that BTS has antioxidative, antifungal activities and cytotoxic effects against Caco-2, Calu-6, SUN-601, HCT-116, AML-2/WT and NIH3T3, especially ethyl acetate fraction from water extract has more effective in antioxidative and anticancer effects.
Journal of the Society of Cosmetic Scientists of Korea
/
v.41
no.3
/
pp.269-277
/
2015
Herbal plant extracts are good resources to find functional compounds for cosmetic ingredient. In this study, the extract of Areca semen (A. semen) was studied for melanogenesis inhibition and antioxidant activity. The results showed that ethyl acetate fraction of A. semen contained phenolic contents, $301.35{\pm}0.88{\mu}g/mg$, and exhibited potent antioxidant activity with $IC_{50}$ value of $1.02{\pm}0.07{\mu}g/mg$. Further, FRAP value exhibited potent antioxidant activity with $9.07{\pm}0.36mM$. Disk diffusion assay was performed for antibacterial activity. Ethyl acetate fraction of A. semen showed antibacterial activity against Staphylococcus aureus (S. aureus) and Staphylococcus epidermidis (S. epidermidis) at $80{\mu}g/mL$, whereas it showed no significant antibacterial activity against Escherichia coli (E. coli). The results of cell viability indicated that ethyl acetate fraction did not show cytotoxicity to B16/F1 cells at $80{\mu}g/mL$ and showed significant cytotoxicity at $100{\mu}g/mL$ of concentration and showed inhibition of melanin synthesis inhibitory, $29.78{\pm}0.31%$ at $80{\mu}g/mL$. Furthermore, mRNA expressions of tyrosinase and MITF were decreased after treatment with ethyl acetate fraction in a dose-dependent manner. As a result, the ethyl acetate fraction of A. semen could be considered as potential as whitening agents.
To screening of antimicrobial activity, 95% ethanol and hot water extracts of roots, fruits, leaves, radix and stems of 50 species of traditional herbal medicines were examined. For their growth inhibitory effects on two food-born microorganisms, S. aureus and E. coli O157:H7, by the paper disc diffusion method and the minimum inhibitory concentration(MIC) test. Moutan radicis Cortex and Achyranthis Radix showed the highest inhibitory activities on both S. aureus and E. coli O157:H7. The Inhibition zones of Moutan radicis Cortex on S. aureus and E. coii O157:H7 were 22 mm and 24 mm respectively, and the corresponding inhibition zone of Achyranthis Radix were 23 mm and 22 mm. The MIC or Achyranthis Radix on S. aureus was 156.25 $\mu$g/mL, and the MIC or Achyranthis Radix and Moutan radicis Cortexas on E. coli O157:H7 were 625 $\mu$g/mL and 312.5 $\mu$g/mL, respectively. Their antimicrobial activities in ethanolic extracts were significantly higher than in hot water extracts. In the various solvent fractions prepared from ethanol extract, the ethyl acetate fraction of Achyranthis Radix and the CHCl$_3$ fraction of Moutan radicis Cortexas showed strongest activity.
Kim, Jung-Eun;Kim, Woo-Yeon;Kim, Ji-Wook;Park, Hyun-Soo;Lee, Seung-Hoon;Lee, Soon-Young;Kim, Min-Ji;Kim, A-Reum;Park, Soo-Nam
Journal of the Society of Cosmetic Scientists of Korea
/
v.36
no.4
/
pp.303-314
/
2010
In this study, the antibacterial, antioxidative effect and component analysis of Pinus koraiensis leaf extracts were investigated. MIC values of the ethyl acetate fraction from P. koraiensis leaf extracts on P. acnes, S. aureus, P. ovale, and E. coli were 0.06 %, 0.25 %, 0.13 % and 0.50 %, respectively. The results showed that the antibacterial activity of the ethyl acetate fraction on P. acnes, P. ovale. and S. aureus was more prominent. The aglycone fraction of P. koraiensis leaf extracts ($22.93\;{\mu}g/mL$) showed more higher free radical (1,1-diphenyl-2-picrylhydrazyl, DPPH) scavenging activity ($FSC_{50}$). Reactive oxygen species (ROS) scavenging activity ($OSC_{50}$) of P. koraiensis leaf extracts on ROS generated in $Fe^{3+}$-EDTA/$H_2O_2$ system was investigated using the luminol-dependent chemiluminescence assay. The 50 % ethanol extract ($0.70\;{\mu}g/mL$) showed the most prominent ROS scavenging activity. Also the ethyl acetate ($1.04\;{\mu}g/mL$) and the aglycone fraction ($1.43\;{\mu}g/mL$) showed very high antoxidant activity. The protective effects of extract/fractions of P. koraiensis leaf extracts on the rose-bengal sensitized photohemolysis of human erythrocytes were investigated. The P. koraiensis leaf extracts showed cellular membrane protective effects in a concentration dependent manner ($5{\sim}50\;{\mu}g/mL$). TLC and HPLC chromatogram of the ethyl acetate fraction obtained from hydrolysis of P. koraiensis leaf extracts revealed 2 main bands (PK-4, PK-6) and peaks (peak 1, peak 2), which were identified as kaempferol-3-O-glucoside (PK-6, peak 1) and kaempferol-3-O-arabinoside (PK-4, peak 2) by LC/ESI-MS/MS, respectively. These results indicate that extract/fractions of P. koraiensis can function as antioxidants in biological systems, particularly skin exposed to UV radiation by scavenging ROS, and protect cellular membrane against ROS. Extract/fractions of P. koraiensis can be applicable to new cosmeceuticals for antioxidant, antiaging, and antibacterial activity.
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