The effect of solvent structure on the slope in the plot of ln K vs. solute carbon number was examined. It was found that the free energy of methylene group transfer from the gas phase into a solvent was always negative and that the absolute magnitude of interaction free energy between the methylene group and the solvent was always larger than the absolute magnitude of cavity formation free energy of the methylene group in the solvent. Thus, the slope in the plot of ln K vs. solute carbon number was always positive and its value decreases with increase of solvent polarity since the cavity formation energy of the CH₂ unit increases with increase of solvent polarity while the dispersive interaction energy of the CH₂ unit is virtually invariant. We also examined the effect of sequential addition of CH₂ unit to a solvent molecule upon ln K for three homologous series of solvents: n-alkanes, n-alcohols, and n-nitriles. Characteristic trends in the plots of ln K vs. solvent carbon number were observed for individual solvent groups. A decrease of ln K with solvent carbon number was observed for n-alkanes. An abrupt increase in ln K followed by levelling off was observed for n-alcohols while a final slight decrease in ln K after an abrupt increase followed by rapid levelling off was noted for n-nitriles. All of theses phenomena were found related to variation in cavity formation energy. It was clearly shown that a structural change of a polar solvent by sequential addition of CH₂ units causes an abrupt polarity decrease initially, then gradual levelling off, and finally, conversion to a virtually nonpolar solvent if enough CH₂ units are added.
Seo, Seung-Ho;Chang, Sung-Hwan;Yoo, Yeoung-Een;Chung, Jae-Dong
Transactions of the Korean Society of Mechanical Engineers B
/
v.35
no.5
/
pp.445-450
/
2011
We studied the adhesion characteristics of polymer films (PC, PET, EVA) treated by atmospheric pressure plasma. The process parameters were the frequency, gas flow, and treatment time; we studied the effects of these parameters on the adhesion characteristics of the polymer materials. We used de-ionized water and diiodomethane as the polar and nonpolar solvents, respectively, for measuring the contact angles, and subsequently calculated the surface free energy of each polymer film. The adhesion characteristics were studied by carrying out a $180^{\circ}$ peel-off test. The polymer films treated with plasma developed a hydrophilic surface, which led to increased surface free energy and improved adhesion properties. From the results for contact angle, surface free energy, and adhesion strength, we obtained the optimal plasma-treatment conditions.
The mixtures of ultra-high molecular weight polythylene (UHMWPE), high density polyethylene (HDPE), process oil (mineral oil) and potassium hexatitanate whisker were melted and mixed at $150^{\circ}C$ for 30min, and prepared by compression molding to the specimen of separator of about $200{\mu}m$ thickness at the same temperature and 5000 psi. Thereafter the pores were formed by extracting process oil with organic solvents. In this study, the range of PR (the ratio polymer to process oil) was varied from 0.1 to 0.5 because the specimen turned into rubbery phase at which PR was below 0.1 whereas it changed into gel phase at which PR was above 0.5. When the specimen was treated with nonpolar organic solvents, process oil was extracted nearly 98%. Tensile strength was $31kg/cm^2$ at PR = 0.426, and resistance of specimen was $37m{\Omega}/cm^2$ at PR = 0.186, and $53m{\Omega}/cm^2$ at PR = 0.426. The $N_2$ adsorption-desorption isotherm showed a hysteresis representing regions of capillary condensation, and the surface area at PR = 0.186 was relatively large as $130cm^2/g$. Potassium hexatitanate whisker was randomly dispersed in between PE layers. It might be that the whisker is intercalated through the PE thin layers oriented by compression.
The study was conducted to investigate the tissue and chemical characteristics of rusty root epidermal cells. In histological study, the rusty symptoms were frequently observed in the epidermis of ginseng root and to be yellow under microscopic observation. Disks of the epidermal cell tissue of the rusty root were usually 2 and 3 times greater in the number of cell layer and thickness of cell wall than the healthy root, respectively. The color degree of methanol extracts from the rusty root epidermis was 5.5 times higher than that of the healthy root. And the extracts of rust matter in the root epidermis were easily dissolved in polar solvents compared to nonpolar solvents. UV-absorption spectra of methanol extracts in various fractions of phenolics showed a maximum peak between 275∼280 nm. The crude lipids and phenolic compounds such as acid insoluble bound phenolics, acid insoluble esterified phenolics, acid insoluble condensed phenolics, insoluble bound phenolics and free phenolics were also more in the rusty root epidermis than in the healthy one. Fe content in the rusty root epidermis was 2.7 times higher than that of healthy one. It was presumed that the phenolic compounds(precursor of the rusty) in association with lipid and iron in the root epidermis might defence the root when ginseng root was depressed by the unfavorable conditions in soil and/or portions of a root system were subjected to anoxic conditions.
Ionic dissociation rates of $\alpha$-chlorobenzyl ethyl ether in each solvent of toluene-$d_8$ and carbon tetrachloride were measured by the method of dynamic NMR spectroscopy. The spin system of these 1H NMR spectra was $AB_3$. The theoretical spectrum was calculated by computer simulation of dynamic NMR spectra, which agreed very well with observed spectra. From this computer simulation, the ionic dissociation rate constant k was obtained, and by Eyring plot with it, slope and intercept length was gained, from which kinetic parameters were calculated.The easiness of ionic dissociation depended upon solvent polarity. Activation enthalpy was 4.7 kcal/mole in toluene-$d_8$, 10.7 kcal/mole in carbon tetrachloride, and activation entropy was -35. 8 e.u. in toluene-$d_8$, -14.4 e.u. in carbon tetrachloride. It was understood that though the ${\Delta}H^{neq}$ value was small, this ionic dissociation had an easier procession in nonpolar solvents with increasing temperatures. Considering that the ionic dissociation could be thought as the first step of $S_N1$ mechanism, attention might be paid to the results that the value of ${\Delta}S^{neq}$ had a large negative value in comparison with a small ${\Delta}H^{neq}$.
Kim, Dong-Wook;Jeong, Hwan-Jeong;Lim, Seok-Tae;Sohn, Myung-Hee
Nuclear Medicine and Molecular Imaging
/
v.43
no.2
/
pp.91-99
/
2009
Noninvasive imaging of molecular and biological processes in living subjects with positron emission tomography(PET) provides exciting opportunities to monitor metabolism and detect diseases in humans. Measuring these processes with PET requires the preparation of specific molecular imaging probes labeled with $^{18}F$-fluorine. In this review we describe recent methods and novel trends for the introduction of $^{18}F$-fluorine into molecules which in turn are intended to serve as imaging agents for PET study. Nucleophilic $^{18}F$-fluorination of some halo- and mesyloxyalkanes to the corresponding $^{18}F$-fluoroalkanes with $^{18}F$-fluoride obtained from an $^{18}O(p,n)^{18}F$ reaction, using novel reaction media system such as an ionic liquidor tert-alcohol, has been studied as a new method for $^{18}F$-fluorine labeling. Ionic liquid method is rapid and particularly convenient because $^{18}F$-fluoride in $H_2O$ can be added directly to the reaction media, obviating the careful drying that is typically required for currently used radiofluorination methods. The nonpolar protic tert-alcohol enhances the nucleophilicity of the fluoride ion dramatically in the absence of any kind of catalyst, greatly increasing the rate of the nucleophilic fluorination and reducing formation of byproducts compared with conventional methods using dipolar aprotic solvents. The great efficacy of this method is a particular advantage in labeling radiopharmaceuticals with $^{18}F$-fluorine for PETimaging, and it is illustrated by the synthesis of $^{18}F$-fluoride radiolabeled molecular imaging probes, such as $^{18}F$-FDG, $^{18}F$-FLT, $^{18}F$-FP-CIT, and $^{18}F$-FMISO, in high yield and purity and in shorter times compared to conventional syntheses.
Proceedings of the Korean Society for Applied Microbiology Conference
/
2001.06a
/
pp.149-153
/
2001
To investigate the mode of bactericidal action for antimicrobial peptide, pediocin, synthetic and mutant pediocins were prepared by direct chemical synthesis. Native pediocin was purified from Pedio-coccus acidilactici M and its conformational structure and bactericidal functions were analyzed and compared to synthetic pediocin. Schematic mode of pediocin actions, how pediocin binds on the target cell membrane, penetrates and makes tunnel are proposed. For these purposes, primary and secondary structures of pediocin was analyzed and disulfide bond assignment was also done. The pediocin purified from P. acidilactici M had high effective bactericidal ability against gram positive bacteria, especially Listeria monocytogenes and was very stable at extreme pHs and even at high temperatures such as autoclaving temperature (121$^{\circ}C$). Pediocin was consisted of 44 amino acids with four cysteines. Novel synthetic peptides were achieved by solid phase peptide synthesis(SPPS) method. To explain the function of cysteine in C-terminal region, mutant pediocin, Ped[C24A+C44A], was synthesized and their structural and biological functions were analyzed. Second mutant pediocin, Ped[KllE], was prepared to explain the function of lysine at 11 of N-terminal part of pediocin, especially loop of $\beta$-sheet, and to predict the initial binding site of pediocin. The native and synthetic pediocins was showed random coil conformation by spectropolarimetry in moderate conditions. This conformation was observed in extreme conditions such as high temperature and low and high pHs, also. Circular dichroism(CD) data also showed the existence of $\beta$-turn structure in N-terminal part both native and synthetic pediocins. A structural model for pediocin predicts that 18 amino acids in the N-terminal part of the peptide assume a three-strand $\beta$-sheet conformation. This random coil in C-terminal part of pediocin was converted to folding structure, helix structure, in nonpolar solvents such as alcohol and TFE. The disulfide bond between $^{9}$ Cys and $^{14}$ Cys was concrete and inevitable, however, evidences of disulfide bond between $^{24}$ Cys and $^{44}$ Cys was not. Data of Ped[C24A+C44A], pediocin mutant showed that $^{44}$ Cys was required during killing the target cells but not inevitable, since Ped[C24A+C44A] still have bactericidal activity but much less than native pediocin. Another pediocin mutant, Ped[KllE], had still bactericidal activity, was controversial to propose that positive charge like as $^{11}$ Lys in loop or hinge in bacteriocin bound or helped to binding to microorganism with electrostatic interaction between cell membrane especially teichoic acid and positive amino acid nonspecifically. The conformation of pediocin among native, synthetic and mutant pediocins did not show big difference. The conformations between oxidized and reduced pediocin were almost similar regardless of native or synthetic.
Fatty acid salts derived from soap can be transferred into a typical derivative with p-bromophenacyl bromide using crown ether, a catalizer by the solid-liquid phase transfer reaction in nonpolar, aprotic solvents and separated by the reverse phase high performance liquid Chromatography (RP-HPLC) and determined using UV detector. The minimal limit of detection was defined at approximately 10~50ng in accordance with the chain length. The derivatization reaction in the presence of EDTA can be applied mot only to the calcium salts but also to the other various metal salts. The recoveries of fatty acid derivatizations in the absence and presence of the midium containing the yeast extract were obtained $95.4{\pm}1.2$, and $85.2{\pm}2.4%$ respectively. The analytical method would be applicable to determine the biodegradation of fatty acid salts in nature as well as in artificial condition such as shaker flask-medium method.
Five types of determination methods including the Soxhlet method as well as 3 kinds of extraction solvents, were used for the determination of accurate crude fat contents in wheat flour and 5 kinds of dry noodles. According to the results, crude fat contents were 0.09~1.37% in the wheat flour and 0.07~1.36% in the dry noodle samples. This variation resulted from the types of lipids in the wheat flour and various kinds of dry noodles. Nutrition facts labels showing crude fat contents in the 5 kinds of domestic dry noodle samples indicated levels of 0~1.5%. Lipid composition and content were determined in order to investigate these differences. The results indicated free lipid at 1.02% and bound lipids at 0.21% in the wheat flour, and free lipids at 0.95~1.01% and bound lipid at 0.21~0.25% in the wheat flour. Polar and nonpolar lipid contents were also measured in all samples. Neutral lipid, glycolipid and phospholipid contents in the free lipid were 58.5%, 33.6%, and 8.6% in the wheat flour, and 49.2~58.2%, 33.3~41.6%, and 8.5~9.3% in the dry noodle samples, respectively. For bound lipids, amounts were 16.7%, 33.5%, and 49.5% in the wheat flour, and 13.2~15.3%, 35.6~45.7%, and 41.6~49.4% in the dry noodle samples, respectively. Based on these results, an acid hydrolysis methods should be used to determine accurate crude fat contents in wheat flour and dry noodles.
The hyperfine splitting constants of phenanthrenequinone anion radical have been determined for the solution of triethylamine with 2-propanol, 2-pentanol or benzene by cwESR and time-resolved ESR methods. The radical anion was produced by photolysis using a pulsed excimer laser. The resulting hyperfine splitting constant A$_{H1}$ and A$_{H2}$ are 1.662, 0.378 in 2-propanol, 1.602, 0.361 in 2-pentanol and 1.518 in benzene respectively. The hyperfine coupling constants decrease with the decreasing of polarity of the mixed solvent. The tendency of the variation depends on the polarity of the solvents, thus, making it in impossible to observe the magnetic equivalent proton in a mixed solvent of nonpolar benzene. Particularly, time-resolved ESR spectrum of triethylamine radical (TEA${\cdot}$) has been observed in 0.15∼0.30 ${\mu}s$ from the solvent of 3 : 1 with 2-pentanol and triethylamine. Thus from the results of solvent effect, we can suggest that the identification of the unstable short-lived spin polarized phenanthrenequinone anion radical(*PQ${\cdot}^-$) proceed through photochemistry.
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