• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2393-2397
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• 2009

Second-order rate constants ($k_{HOO}$‒) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted phenyl benzenesulfonates (1a-g) with $HOO^-$ ion in $H_2O$ at $25.0\;{\pm}\;0.1\;{^{\circ}C}$. The Br$\phi$nsted-type plot is linear with ${\beta}_{lg}$ = ‒0.73. The Hammett plot correlated with with ${\sigma}^-$ constants results in much better linearity than ${\sigma}^o$ constants, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS) either in a stepwise mechanism or in a concerted pathway. However, a stepwise mechanism in which departure of the leaving group occurs in the RDS has been excluded since $HOO^-$ ion is more basic and a poorer leaving group than the leaving Y-substituted phenoxide ions. Thus, the reactions of 1a-g with $HOO^-$ ion have been concluded to proceed through a concerted mechanism. The $\alpha$-nucleophile $HOO^-$ ion is more reactive than its reference nucleophile $OH^-$ ion although the former is ca. 4 p$K_a$ units less basic than the latter (i.e., the $\alpha$-effect). TS stabilization through intramolecular H-bonding interaction has been suggested to be irresponsible for the $\alpha$-effect shown by $HOO^-$ ion, since the magnitude of the $\alpha$-effect is independent of the electronic nature of substituent Y in the leaving group. GS destabilization through desolvation of $HOO^-$ ion has been concluded to be responsible for the $\alpha$-effect found in the this study.

• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1089-1096
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• 2002

Solvolyses rate constants of trimethylacetyl chloride (2), isobutyryl chloride (3), diphenylacetyl chloride (4) and p-methoxyphenylacetyl chloride (5) in 2,2,2-trifluoroethanol (TFE)-water, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water and TFE-et hanol solvent systems at $10^{\circ}C$ are determined by a conductimetric method. Kinetic solvent isotope effects (KSIE) are reported from additional kinetic data for methanolyses of various substituted acetylchlorides in methanol According to the results of those reactions analyzed in terms of rate-rate profiles,extended Grunwald-Winstein type correlations, application of a third order reaction model based a general base catalyzed (GBC) and KSIE values. Regardless of the kind of neighboring groups (CH3- or Ph-groups) of reaction center, for aqueous fluorinated alcohol systems, solvolyses of 2, 3, 4, and 5 were exposed to the reaction with the same mechanism (a loose SN2 type mechanism by electrophilic solvation) controlled by a similarity of solvation of the transition sate (TS). Whereas, for TFE-ethanol solvent systems, the reactivity depended on whether substituted acetyl chloride have aromatic rings (Ph-) or alkyl groups (CH3-); the solvations by the predominant stoichiometric effect (third order reaction mechanism by GBC and/or by push-pull type) for Ph- groups (4 and 5) and the same solvation effects as those shown in TFE-water solvent systems for CH3- groups (2 and 3) were exhibited Such phenomena can be interpreted as having relevance to the inductive effect ( $\sigmaI)$ of substituted groups; the plot of log (KSIE) vs. ${\sigma}I$ parameter give an acceptable the linear correlation with r = 0.970 (slope = 0.44 $\pm$ 0.06, n = 5).

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.201-206
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• 2013

The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. A linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${\o}$nsted-type plot, implying that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${\alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${\alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${\alpha}$-effect for the reaction of the more polarizable substrate 2.

• Korean Journal of Applied Biomechanics
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• v.24 no.2
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• pp.95-101
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• 2014

The purpose of this study was to investigate the training and detraining effects of a 8-week water exercise on lower extremities coordination during obstacle gait in the female elderly. Eight elderly participants (age: $76.58{\pm}4.97$ yrs, height: $148.88{\pm}7.19$ cm, body mass: $56.62{\pm}6.82$ kg, and leg length: $82.36{\pm}2.98$ cm), who stayed at the Seoul K welfare center, were recruited for this study. All participants had no history of orthopedic abnormality within the past 1 year and completed the aquatic exercise program which lasted for 8 weeks. To identify the training and detraining effect of 8 weeks of water exercise, a 3-D motion analysis with 7 infrared cameras and one force plate sampling frequency set at 100 Hz and 1,000 Hz, respectively, was performed. A two-way ANOVA was performed to find training and detraining effects among diferent obstacle heights. In this study significant level was set at .05. Significant training effects of LTS (lead foot thigh and shank) coordination in all obstacle height were found (p<.05). It is also found that the training effect of LTS remained 37%, 58%, and 25% in obstacle height of 30%, 40%, and 50%, respectively. Lead foot showed the greater detraining effect of coordination compared with trail foot, and SF (shank and foot) coordination revealed better detraining effects of coordination compare with TS (thigh and shank) in both feet. Based on the findings, a 8 week water exercise give an positive effects to the elderly in terms of segment cooperation which potentially helps reducing their accident falls. The magnitude of detraining may also help the elderly to find the retraining moment.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.802-807
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (＋0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

• Tissue Engineering and Regenerative Medicine
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• v.15 no.6
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• pp.711-719
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• 2018

BACKGROUND: Collagen organization within tissues has a critical role in wound regeneration. Collagen fibril diameter, arrangements and maturity between connective tissue growth factor (CTGF) small interfering RNA (siRNA) and mismatch scrambled siRNA-treated wound were compared to evaluate the efficacy of CTGF siRNA as a future implement for scar preventive medicine. METHODS: Nanocomplexes of CTGF small interfering RNA (CTGF siRNA) with cell penetrating peptides (KALA and $MPG^{{\Delta}NLS}$) were formulated and their effects on CTGF downregulation, collagen fibril diameter and arrangement were investigated. Various ratios of CTGF siRNA and peptide complexes were prepared and down-regulation were evaluated by immunoblot analysis. Control and CTGF siRNA modified cells-populated collagen lattices were prepared and rates of contraction measured. Collagen organization in rabbit ear 8 mm biopsy punch wound at 1 day to 8 wks post injury time were investigated by transmission electron microscopy and histology was investigated with Olympus System and TS-Auto software. CONCLUSION: CTGF expression was down-regulated to 40% of control by CTGF siRNA/KALA (1:24) complexes (p<0.01) and collagen lattice contraction was inhibited. However, down-regulated of CTGF by CTGF $siRNA/MPG^{{\Delta}NLS}$ complexes was not statistically significant. CTGF KALA-treated wound appeared with well formed-basket weave pattern of collagen fibrils with mean diameter of $128{\pm}22nm$ (n = 821). Mismatch siRNA/KALA-treated wound showed a high frequency of parallel small diameter fibrils (mean $90{\pm}20nm$, n = 563). CONCLUSION: Controlling over-expression of CTGF by peptide-mediated siRNA delivery could improve the collagen orientation and tissue remodeling in full thickness rabbit ear wound.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.36 no.2
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• pp.143-150
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• 2023

Underwater wireless communication is a challenging issue for realizing the smart aqua-farm and various marine activities for exploring the ocean and environmental monitoring. In comparison to acoustic and radio frequency technologies, the visible light communication is the most promising method to transmit data with a higher speed in complex underwater environments. To send data at a speedier rate, high-performance photodetectors are essentially required to receive blue and/or cyan-blue light that are transmitted from the light sources in a light-fidelity (Li-Fi) system. Here, we fabricated high-performance organic phototransistors (OPTs) based on P-type donor polymer (PTO2) and N-type acceptor small molecule (IT-4F) blend semiconductors. Bulk-heterojunction (BHJ) PTO2:IT-4F photo-active layer has a broad absorption spectrum in the range of 450~550 nm wavelength. Solution-processed OPTs showed a high photo-responsivity >1,000 mA/W, a large photo-sensitivity >10³, a fast response time, and reproducible light-On/Off switching characteristics even under a weak incident light. BHJ organic semiconductors absorbed photons and generated excitons, and efficiently dissociated to electron and hole carriers at the donor-acceptor interface. Printed and flexible OPTs can be widely used as Li-Fi receivers and image sensors for underwater communication and underwater internet of things (UIoTs).

• Korean Journal of Poultry Science
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• v.23 no.1
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• pp.27-37
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• 1996

This experiment was carried out to study the effects of feeding split diets for a.m. and p.m. on laying hen performance and feed cost with 480 ISA Brown layers for three periods during 32∼36, 52∼56 and 72∼76 wk of age, respectively. The control group(C) was fed a conventional single diet throughout the day and split diet groups (T$_1$, T$_2$, T$_3$, T$_4$ and T$\_$5/) were offered high energy-high protein-low Ca diets, and low energy-low protein-high Ca diets in a.m. and p.m., respectively. In split diet groups, feed intake, ME and CP consumption, and feed cost were significantly reduced(P<0.05) compared to the C, while the hen-day egg production was significantly improved. However, the average egg weight was not influenced by the feeding system. Due to the reduced daily feed, ME, and CP intakes, and the improved egg production, the conversions of feed, ME, CP, and feed cost required per kg egg mass were also significantly improved (P<0.05) in splits diet groups. Among split diet groups, the T$_2$ group fed the diet devoid of Ca supplement from the conventional laying hen diet in a.m., and the diet containing the Ca supplement 2 times the conventional diet in p.m., was superior in conversion of nutrients and feed cost per kg egg mass to the other split diet groups. It was concluded that daily feed and nutrients cousumption and daily feed cost could be reduced 5∼6％ while hen-day egg production could be improved about 4％, so that about 10％ of the feed and nutrients and feed cost per kg egg mass could be spared by introducing the split diet feeding for a.m. and p.m. based on T$_2$ treatment in laying hens.

• Journal of Animal Science and Technology
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• v.44 no.2
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• pp.239-250
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• 2002

Evaluation works of oat in mixture with rye on forage yield have not been reported. The objective of this study was to determine yield and quality of forage mixture as affected by maturity of rye cultivar and oat-rye seeding rate at Suweon from 1999 to 2000. The experiment was arranged in a split plot design with three replications. Main plots consisted of maturity of rye. such as early(cv. Koolgrazer) and late(cv. Kodiak)maturing cultivars. Sub-plots consisted of seeding rate (T1: Oat 2000 and rye 0kg/ha, Ts: Oat 150 and rye 40kg/ha, T3: Oat100 and rye 80kg/ha, T4: Oat50 and rye 120kg/ha. and T5: Oat0 and rye 160kg/ha). Crude protein(CP) content of oat-rye mixture harvested in the fall was not influenced by maturity of rye cultivar, but that of oat-rye mixture was increased from 13.6 to 19.3% as the seeding rate of rye increased(P<0.05), however, maturity of rye cultivar significantly affected CP content of oat-rye mixture in the spring(P<0.01). Acid detergent fiber(ADF) content of oat-rye mixture harvested in the spring was not significantly affected by rye cultivar, but the ADF was decreased from 27.8 to 20.7% as the seeding rate of rye increased(P$<$0.01). When rye was harveste in the spring, ADF content of late maturing cultivar 'Kodiak' was shown as 28.0%. This was lower than that of early maturing cultivar 'Koolgrazer' which was shown as 35.8%(P$<$0.01). Among treatments, neutral detergent fiber(NDF) and in vitro dry matter digestibility(IVDMD) of oat-rye mixture showed a similar trend made on ADF. In this experiment, the highest forage yield (12.356kg/ha) was obtained from early maturing rye cultivar and seeding rates of 100kg/ha of oat and 80kg/ha of rye mixture. A significant interaction between maturity of rye cultivar and seeding rate was found(P$<$0.01). The above results indicate that an early maturing rye cultivar at the seeding rate of 100kd/ha in mixtures with 80kg/ha of oat could be recommended as a succeeding cropping system after corn for silage.

• Journal of fish pathology
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• v.6 no.2
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• pp.93-101
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• 1993

The RNAI mutation of Saccharomyces cerevisia is a recessive and temperature sensitive lethal mutation which interferes with the production of mRNA, rRNA, and tRNA. However, the precise role of RNAI gene have not been revealed until yet. We have cloned rna1-1 mutant gene from rna1-1 mutant yeast strain(R49 ; trpl, ura3-52, rna1-1). The 3.4kb BglII fragment of wild type RNAI clone(81-2-6) contains whole RNAI gene. The genomic southern blotting with BglII digested R49 genomic DNA as a probe shows the unique and identical band with wild type 3.4kb BglII fragment. Therefore, We prepared partial BglII genomic library(3~4kb BglII fragments) into BamH I site of pUC19. The rna 1-1 mutant clone was screened with Digoxigenin(DIG)-lableled probe by high density colony hybridization. The 5'-flanking region of rna1-1 gene was sequenced by dideoxy chain termination method. The 5'-flanking sequence of RNAI gene contains three TATA-like sequence ; TAATA, TATA and TTTTAA at position of -67, -45, and -36 from first ATG codon respectively. The 5'-flanking region of wild type RNA I gene from ATG codon to -103nt was deleted with Bal31 exonuclease digestion, generating $pUC{\Delta}$/RNA I. After constructing $pYEP{\Delta}RNA$ I (consists of -103nt deleting RNA I gene, URA3 gene, $2{\mu}m$ rep. origin), pYEPrna1-1(consists of Xba I fragment of pUCrna1-1. URA3 gene, $2{\mu}m$ rep. origin), and pYEPRNAI. each plasmid was transformed into host strain(trpl, ura3-52, rna1-1) by electroporation, respectively. Yeast transformant carrying $pYEP{\Delta}RNA$ I did not complement the thermal sensitivity of rna1-1 gene. It means that TATA-like sequences in 5'-flanking region is not TATA sequence for transcribing RNAI gene and there may be other essential sequence in upstream region for the transcription of RNAI gene.