Oleyl alcohol, butyl butyrate, and two different ionic liquids were evaluated for the extraction of butanol from culture broth without toxic effect to cells. The tested solvents showed more than 50% extraction efficiency, and oleyl alcohol was chosen as the best extractant for butanol among the used extractants with a partition coefficient of 2.89. When oleyl alcohol was used as an extractant, more than 80% of butanol was extracted in the wide range of butanol concentrations (1-20 g/L) and pH values (pH 4-5.5). In extractive fermentation using oleyl alcohol only, there was 11% more butanol production and glucose consumption when compared to that without extractive fermentation, implicating a reduced inhibitory effect of butanol due to butanol removal to the oleyl alcohol phase. In addition, oleyl alcohol did not inhibit cell growth, while a mixture of oleyl alcohol and butyl butyrate with the volume ratio of 9:1~7:3 inhibited either butanol production or cell growth significantly due to the toxicity of butyl butyrate to cells. In conclusion, oleyl alcohol can be used as an efficient and non-toxic solvent for extractive fermentation for butanol production.
Partitioning of two hydrophobic organic compounds (HOCs), phenanthrene and naphthalene, to kaolinite and sorbed surfactants was studied to evaluate the feasibility of surfactant-enhanced remediation (SER) of contaminated subsurface systems. Sorbed surfactant partition coefficients. $K_ss$, showed a strong dependence on the surfactant sorption isotherms at low sorbed surfactant levels $K_ss$ values were at their highest and then decreased with increasing surfactant sorption densities. $K_ss$ values for SDS were always larger than corresponding $K_mic$values. For Tween 80, however. $K_ss$ values $K_mic$ were higher than $K_mic$ values only at the lower sorbed surfactant densities. HOC distribution between immobile and mobile phases varied with surfactant dose distribution coefficients increased initially with increasing surfactant concentrations and then decreased at higher doses. This observation shows directly the competition between sorbed and micellar surfactants for HOC partitioning. Overall results of this study demonstrate that surfactant sorption to the solid phase can lead to increases in HOC retardation in some SER applications. Therefore, before an SER process is selected, appropriate consideration of surfactant sorption and HOC partitioning to immobile versus mobile phases pertinent to a specific subsurface system must be contemplated.
Although liposome has many advantages as a pharmaceutical dosage form, its application in the industrial field has been limited because of some problems such as preparation method, reproducibility, scale-up, stability and sterilization etc. Liposomes prepared by microemulsification method had defined size, narrow size distribution, reproducibility and high entrapment efficiency. For enhancing the stability, the dry form of liposome was recommended. These types of liposome are proliposome and freeze-dried liposome. The liposome must have some properties for preparing of freeze-dried liposome; small size $(50{\sim}200\;nm)$, narrow size distribution and cryoprotectant. In this experiment, the liposomes containing 5-Fluorouracil(5-FU) and its prodrug(pentyl-5-FU-1-acetate; PFA, hexyl-5-FU-1-acetate; HFA) were made with soybean phosphatidylcholine, cholesterol, stearylamine(SA) and dicetyl phosphate(DCP) employing hydration method or microemulsification method using $Microfluidizer^{TM}$. Both or liposome types were MLV and MEL. After preparation, freeze drying and rehydration were performed. In the process of freezing, trehalose(Tr) was added as a cryoprotectant. Their evaluation methods were as follows; entrapment efficiency, mean particle size and size distribution, dissolution test, retain of entrapment efficiency and turbidity after freeze-drying. The results are summarized as belows. The entrapment efficiency of 5-FU was dependent on total lipid concentration and cholesterol content but that of PFA and HFA was decreased when cholesterol was added. When DCP and SA were added, entrapment efficiency was decreased. As the partition coefficient of drug was increased, entrapment efficiency was increased. Under the same condition, entrapment efficiency of MEL is similar to that of MLV. The mean particle size and size distribution of MEL were smaller than those of MLV. Dissolution rates of drug from both liposome types were comparatively similar. Dissolution rates of drugs with serum and liver homogenate were faster than without these material. After preparation of liposome, free drug was removed efficiency by Dowex 50W-X4. When liposome was freeze-dried and then rehydrated in the presence of Tr, characteristics of liposome were maintained well in MEL than MLV. Tr Was used successfully as a cryoprotectant in the process of freeze drying and the optimal ratio of Tr:Lipid was 4:1(g/g).
We investigated metal concentrations and oceanic environment changes that have occurred over the past several years by studying the hard coral Porites lutea, which inhabits tropical and subtropical areas. Soft X-radiographs clearly showed distinctive annual bands within 71 mm coral sample, which reflect changes in the oceanic environment over this period. There were large fluctuations in the major and minor element concentrations. Considering the physicochemical partition coefficient, some elements accumulated in the aragonite matrix in a mechanical manner, while others were affected by environmental factors. The concentrations of some heavy metals varied over a wide range, implying local environmental effects. The variation of Sr/Ca and Mg/Ca in coral skeleton clearly showed large-scale fluctuation over the specific intervals, implying environmental changes during this period. The concentrations of heavy metals also show high fluctuations, and roughly accord with Mg/Ca variation. In addition, Cu and Zn seem to show cyclicity-like peaks, coincide with Mg/Ca variation over the specific intervals. Such variation might be related to local pollution and oceanographic changes. More detailed investigation is necessary, including the pretreatment of coral skeleton sediment.
Biphenyldimethyldicarboxylate (PMC), which has been used to treat hepatitis, is insoluble in water, therefore it has low bioavailability after oral administration. For the purpose of increasing the dissolution rate of PMC, the physical mixtures and inclusion complexes of PMC and $dimethyl-{\beta}-cyclodextrin\;(DM\;{\beta}CD)\;or\;hydroxypropyl-{\beta}-cyclodextrin\;(HP{\beta}CD)$ in molar ratio of 1 : 1 and 1 : 2 were prepared by solvent evaporation method. Mixed micelles of PMC were prepared by reacting PMC with bile salts [sodium cholate(NaC), sodium glycocholate (NaGC)] and oleic acid (OA) or palmitoylcarnitine chloride(PCC). Chloroform/water partition coefficient (PC) of PMC was 36.14 in artificial gastric juice (AGJ) and 33.47 in artificial intestinal juice (AIJ), respectively, on the other hand octanol/water PC was 63.36. PMC formulation was prepared by reacting PMC with PEG400-glycerin system(95 : 5, 90 : 10, respectively) and PEG400-PEG4000-glycerin system (70 : 25 : 5, 65 : 25 : 10, respectively). Dissolution test was performed in AGJ and AIJ by paddle method at $37{\pm}0.5^{\circ}C$. The dissolution rates of PMC tablets on the market were 5.74% and 8.26% at AGJ and AIJ, respectively and marketed PMC capsules were 22.14% and 28.64% at AGJ and AIJ, respectively. The dissolution rates of inclusion complexes of PMC with $DM{\beta}CD$ and $HP{\beta}CD$ in a molar ratio of 1 : 1 were more fast than those of corresponding physical mixtures. The decreasing order of dissolution rates was as follows; PMC-PEG400-PEG4000-glycerin formulation > PMC-PEG400-glycerin formulation > mixed micelles > CD inclusion complexes. The dissolution rates of PMC-PEG400-glycerin and PMC-PEG400-PEG4000-glycerin formulation were most fast and the percentage of dissolution was almost 100% within 20 minutes. And their dissolution rates after 120 minutes were markedly increased as compared with capsules on the market (4.0-fold and 3.2-fold in PMC-PEG400-glycerin formulation at AGJ and AIJ, respectively, and 4.8-fold and 3.7-fold in PMC-PEG400-PEG4000-glycerin formulation at AGJ and AIJ, respectively).
Park, Kang Hoon;Park, Chang Kyu;Park, Jong;Jeon, Seungho;Bang, Sa-Ik;Kim, Ji-Heung;Chung, Dong June
Polymer(Korea)
/
v.38
no.3
/
pp.333-337
/
2014
PVC (polyvinyl chloride) intravenous fluid bags and tubes that contain DEHP (diethylhexyl phthalate) as a plasticizer have several associated disadvantages for intravenous injections. We investigated the drug absorption behaviors on the inner surface of an infusion tube that consisted of commercialized PVC/PU (polyurethane). We developed a non-PVC (polyolefin) tube in order to improve the efficacy of this drug administration method. We prepared four types of non-PVC (polyolefin) infusion tubes using a polyethylene (PE), polypropylene (PP), syndiotactic 1,2-polybutadiene (PB), and styrene-ethylene (SE) copolymer elastomers were prepared using a single screw extruder. The four types of manufactured non-PVC (polyolefin) infusion tubes had good mechanical properties that were equivalent to PVC tube properties. The four types of prepared non-PVC (polyolefin) infusion tubes also prohibited drug absorption when compared to the commercialized PVC and PU tubes. Therefore, based on the results of this study, prepared non-PVC (polyolefin) tubes are good candidates for infusion because they prevent drug absorption and the release of DEHP.
This study was performed to investigate the bioconcentration of IBP, methidathion and piperophos. The BCFs(bioconcentration factor), depuration rate constants for three pesticides in zebrafish(Brachydanio rerio) were measured by OECD guideline 305. The concentration of test pesicides were one-hundredth and one-thousandth concentration of 96-hrs L $C_{50}$ in accordance with OECD guideline 305. The results obtained are summarized as follows: The average BCF values of IBP were 5.31(n=4) and 7.30(n=4) at one-hundredth and one-thousandth concentration of 96-hrs L $C_{50}$ . The average BCF values of methidathion were 8.72(n=4) and 11.25(n=4), the average BCF values of piperophos were 34.30(n=4) and 42.60(n=4). Depuration rate constants of IBP were 0.09( $h^{-1}$ ) and 0.08( $h^{-1}$ ), half-life of IBP were 7.70 and 8.66 at each tested concentration. The concentrations of IBP in zebrafish at low and high concentrations rapidly decreased after 12(0.243$\mu\textrm{g}$/g) and 12 hours(0.040$\mu\textrm{g}$/g). Depuration rate constants of methidathion were 0.40( $h^{-1}$ ), half-life of methidathion were 1.73 at one-hunderdth and of 96-hrs L $C_{50}$ , repectively. The concentrations of methidathion in zebrafish at high concentrations rapidly decreased after 6 hours(0.18 $\mu\textrm{g}$/g). Depuration rate constant of low concentration was no measured because methidathion in zebrafish was depurated in 6 hours. Depuration rate constants of piperophos sere 0.15( $h^{-1}$ ) and 0.44( $h^{-1}$ ), half-life of piperophos were 4.62 and 1.58 at each tested concentration. The concentrations of piperophos in zebrafish at los and high concentrations rapidly decreased after 12(0.26$\mu\textrm{g}$/g) and 6 hours(0.015 $\mu\textrm{g}$/g). It was suggested that high BCF of piperophos was due to high Kow(octanol-water partition coefficient). The possibility of bioconcenration was not likely to be high because of its $K_{DEP}$(depuration rate constant) in the evniroment. It was suggested that low BCF of methidathion showed lowest Kow as well as the most rapid $K_{DEP}$. Therefore, the possibility of bioconcentration was not occured in the enviroment. It was suggested that the BCF dtermined for IBP was lower than that of other pesticides due to high Sw(water solubility), show $K_{DEP}$. Therefore, IBP revealed little bioconcentration effect on in aquatic ecosystem.ystem.
Strawberries are one of the main commodities in Korea and have been exported over 40 million dollar. Because the strawberry cultivation using hydroponics has increased, treatment of pesticide by drenching draw interest recently. However, detailed researches for drenching treatment of pesticide are limited, which results in difficulties in proper pesticide applications in agricultural fields. To activate use of drenching and improve safety in agricultural products, In this study, time-dependent residual characteristic of pesticides were compared with between different applications of pesticides in strawberries. The characteristics of azoxystrobin, prochloraz and thiamethoxam were investigated with drenching treatment at different applications: the time of treatment, concentration etc. at hydroponic cultivation for 40 days. Azoxystrobin and prochloraz were not detected at 14 day after application. Thiamethoxam was detected from 0.02 to 0.85 mg/kg. Crop uptake of pesticides was strongly affected with octanol-water partition coefficient and solubility in water. Residual amount in crops are highly dependent on the concentration of active ingredient of pesticides.
Kim, Dongwoo;Lee, Seungchel;Kim, Minjeong;Lee, Eunji;Yoo, ChangKyoo
Korean Chemical Engineering Research
/
v.54
no.5
/
pp.621-629
/
2016
Recently, the researches on quantitative structure activity relationship (QSAR) for describing toxicities or activities of chemicals based on chemical structural characteristics have been widely carried out in order to estimate the toxicity of chemicals in multiuse facilities. Because the toxicity of chemicals are explained by various kinds of molecular descriptors, an important step for QSAR model development is how to select significant molecular descriptors. This research proposes a statistical selection of significant molecular descriptors and a new QSAR model based on partial least square (PLS). The proposed QSAR model is applied to estimate the logarithm of partition coefficients (log P) of 130 polychlorinated biphenyls (PCBs) and lethal concentration ($LC_{50}$) of 14 PCBs, where the prediction accuracies of the proposed QSAR model are compared to a conventional QSAR model provided by OECD QSAR toolbox. For the selection of significant molecular descriptors that have high correlation with molecular descriptors and activity information of the chemicals of interest, correlation coefficient (r) and variable importance of projection (VIP) are applied and then PLS model of the selected molecular descriptors and activity information is used to predict toxicities and activity information of chemicals. In the prediction results of coefficient of regression ($R^2$) and prediction residual error sum of square (PRESS), the proposed QSAR model showed improved prediction performances of log P and $LC_{50}$ by 26% and 91% than the conventional QSAR model, respectively. The proposed QSAR method based on computational toxicology can improve the prediction performance of the toxicities and the activity information of chemicals, which can contribute to the health and environmental risk assessment of toxic chemicals.
BACKGROUND: In order to elucidate residual characteristics of difenoconazole and thiamethoxam by treatment to sweet persimmons for one year and to generate the data for the maximum residue limit (MRL) establishment for those pesticides in or on sweet persimmon. METHODS AND RESULTS: Systemic fungicide difenoconazole WP (10% a.i.) and systemic insecticide thiamethoxam WG (10% a.i.) were sprayed onto 12~25-years-old sweet persimmons according to its preharvest interval (PHI), respectively, and then fresh sweet persimmons were harvested at 0, 1, 3, 7, 14, 21 days after treatment from pesticide-sprayed plots at each 3 sites. The analytical methods were evaluated to limit of quantification, linearity, specificity, reproducibility and recoveries. The crop samples were extracted with acetone and performed dichloromethane partition process. The extracted samples of difenoconazole were analyzed by GC-ECD and the thiamethoxam extracted samples were analyzed by HPLC with good sensitivity and selectivity of the method. The average recoveries of difenoconazole ranged from 87.5 to 99.5% with the percentage of coefficient variation in the range 4.1~7.6% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg). And the average recoveries of thiamethoxam and clothianidin ranged from 88.8 to 98.9% and 83.2 to 96.6% with the percentage of coefficient variation in the range 3.6~5.0% and 3.8~9.4% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg), respectively. The residue amounts ranges of difenoconazole were 0.2~0.56 mg/kg and the residue amount was decreased below the MRL level, 1.0 mg/kg, after 1 day harvest. The residue amounts ranges of thiamethoxam were 0.08~0.28 mg/kg and the residue amount was decreased below the MRL level, 0.5 mg/kg, after 1 day harvest. And the residue amount of clothianidin was below then 0.03 mg/kg for only one test site of 14 and 28 day samples. CONCLUSION: As a result, the residual amounts of difenoconazole and thiamethoxam were not exceeded the MRL of established criteria for sweet persimmon. The biological half-lives of difenoconazole and thiamethoxam were 13.6, 19.4, 16.3 and 10.0, 15.3, 14.0 days at each three test sites, respectively.
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