• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3795-3799
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• 2013

The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

• Journal of the Korean Vacuum Society
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• v.6 no.1
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• pp.9-19
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• 1997

The reaction mechanisms of dry cleaning with UV-excited chlorine radical for Zn, Fe and Ti trace contaminants on the Si wafer have been studied by SEM, AFM and XPS analyses in this work. The patterned Zn, Fe and Ti films were deposited on the Si wafer surface by thermal evaporation and changes in the surface morphology after dry cleaning with $Cl_2$and UV/$Cl_2$at $200^{\circ}C$ were studied by optical microscopy and SEM. In addition, changes in the surface roughness of Si wafer with the cleaning was observed by AFM. The chemical bonding states of the Zn, Fe and Ti deposited silicon surface were observed with in-line XPS analysis. Zn and Fe were easily cleaned in the form of volatile zinc-chloride and iron-chloride as verified by the surface morphology changes. Ti which forms involatile oxides was not easily removed at room temperature but was slightly removed by UV/$Cl_2$at elevated temperature of $200^{\circ}C$. It was also found that the surface roughness of the Si wafer increased after $Cl_2$and UV/$Cl_2$cleaning. Therefore, the metallic contaminants on the Si wafer can be easily removed at lower temperature without surface damage by a continuous process using wet cleaning followed by UV/$Cl_2$dry cleaning.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.27-27
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• 2011

For the design of real applicable molecular devices, current-voltage properties through molecular nanostructures such as metal-molecule-metal junctions (molecular junctions) have been studied extensively. In thiolate monolayers on the gold electrode, the chemical bonding of sulfur to gold and the van der Waals interactions between the alkyl chains of neighboring molecules are important factors in the formation of well-defined monolayers and in the control of the electron transport rate. Charge transport through the molecular junctions depends significantly on the energy levels of molecules relative to the Fermi levels of the contacts and the electronic structure of the molecule. It is important to understand the interfacial electron transport in accordance with the increased film thickness of alkyl chains that are known as an insulating layer, but are required for molecular device fabrication. Thiol-tethered RuII terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Electrochemical voltammetry and current-voltage (I-V) characteristics are measured to elucidate electron transport processes in the bistable conducting states of single molecular junctions of a molecular switch, Ru(II) terpyridine complexes. (1) On the basis of the Ru-centered electrochemical reaction data, the electron transport rate increases in the mixed self-assembled monolayer (SAM) of Ru(II) terpyridine complexes, indicating strong electronic coupling between the redox center and the substrate, along the molecules. (2) In a low-conducting state before switch-on, I-V characteristics are fitted to a direct tunneling model, and the estimated tunneling decay constant across the Ru(II) terpyridine complex is found to be smaller than that of alkanethiol. (3) The threshold voltages for the switch-on from low- to high-conducting states are identical, corresponding to the electron affinity of the molecules. (4) A high-conducting state after switch-on remains in the reverse voltage sweep, and a linear relationship of the current to the voltage is obtained. These results reveal electron transport paths via the redox centers of the Ru(II) terpyridine complexes, a molecular switch.

• The Journal of Korean Academy of Prosthodontics
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• v.45 no.5
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• pp.601-610
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• 2007

Statement of problem: The adhesion between titanium and ceramic is less optimal than conventional metal-ceramic bonding, due to reaction layer form on cast titanium surface during porcelain firing. Purpose: This study characterized the effect of titanium-ceramic adhesion after gold and TiN coating on cast and wrought titanium substrates. Material and method: Six groups of ASTM grade II commercially pure titanium and cast titanium specimens$(13mm{\times}13mm{\times}1mm)$ were prepared(n=8). The conventional Au-Pd-In alloy served as the control. All specimens were sandblasted with $110{\mu}m\;Al_2O_3$ particles and ultrasonically cleaned for 5min in deionized water and dried in air before porcelain firing. An ultra-low-fusing dental porcelain (Vita Titankeramik) was fused on titanium surfaces. Porcelain was debonded by a biaxial flexure test at a cross head speed of 0.25mm/min. The excellent titanium-ceramic adherence was exhibited by the presence of a dentin porcelain layer on the specimen surface after the biaxial flexure test. Area fraction of adherent porcelain (AFAP) was determined by SEM/EDS. Numerical results were statistically analyzed by one-way ANOVA and Student-Newman-Keuls test at ${\alpha}=0.05$. Results: The AFAP value of cast titanium was greatest in the group 2 with TiN coating, followed by group 1 with Au coating and the group 3 with $Al_2O_3$ sandblasting. Significant statistical difference was found between the group 1, 2 and the group 3 (p<.05). The AFAP value of wrought titanium was greatest in the group 5 with TiN coating, followed by the group 4 with Au coating and the group 6 with $Al_2O_3$ sandblasting. Conclusion: No significant difference was observed among the three groups (p>.05). The AFAP values of the cast titanium and the wrought titanium were similar. However the group treated with $Al_2O_3$ sandblasting showed significantly lower value (p<.05).

• Macromolecular Research
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• v.10 no.3
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• pp.158-167
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• 2002

In order to endow with new bioactive functionality from small intestine submucosa (SIS) powder as natural source to poly (L-lactide) (PLA) and poly (lactide-co-glycolide) (PLGA) synthetic biodegradable polymer, porous SIS/PLA and SIS/PLGA as natural/synthetic composite scaffolds were prepared by means of the solvent casting/salt leaching methods for the possibility of the application of tissue engineered bone and cartilage. A uniform distribution of good interconnected pores from the surface to core region was observed the pore size of 40~500 ${\mu}{\textrm}{m}$ independent with SIS amount using the solvent casting/salt leaching method. Porosities, specific pore areas as well as pore size distribution also were almost same. After the fabrication of SIS/PLA hybrid scaffolds, the wetting properties was greatly enhanced resulting in more uniform cell seeding and distribution. Five groups as PGA non-woven mesh without glutaraldehyde (GA) treatment, PLA scaffold without or with GA treatment, and SIS/PLA (Code No.3 ; 1 : 12 of salt content, (0.4 : 1 of SIS content, and 144 ${\mu}{\textrm}{m}$ of median pore size) without or with GA treatment were implanted into the back of nude mouse to observe the effect of SIS on the induction of cells proliferation by hematoxylin and eosin, and von Kossa staining for 8 weeks. It was observed that the effect of SIS/PLA scaffolds with GA treatment on bone induction are stronger than PLA scaffolds, that is to say, in the order of PLA/SIS scaffolds with GA treatment > PLA/SIS scaffolds without GA treatment > PGA nonwoven > PLA scaffolds only with GA treatment = PLA scaffolds only without GA treatment for the osteoinduction activity. The possible explanations are (1) many kinds of secreted, circulating, and extracellular matrix-bound growth factors from SIS to significantly affect critical processes of tissue development and differentiation, (2) the exposure of SIS to GA resulted in significantly calcification, and (3) peri-implant fibrosis due to covalent bonding between collagen molecule by crosslinking reaction. In conclusion, it seems that SIS plays an important role for bone induction in SIS/PLA scaffolds for the application of tissue engineering area.

• Journal of the Korean Electrochemical Society
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• v.7 no.4
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• pp.173-178
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• 2004

Silicon thin film were synthesized from silane and argon gas mixture directly on copper foil by rf PECVD and then lithium ion batteries were prepared from them employed as the negative electrodes without any further treatment. In the present study, two different kinds of silicon thin films, amorphous silicon and copper silicide were prepared by changing deposition temperature. Amorphous silicon film was prepared below $200^{\circ}C$, but copper silicide film with granular shape was formed by the reaction between silicon radical and diffused copper ions under elevating temperature above $400^{\circ}C$. The amorphous silicon film gives higher capacity than copper silicide, but the capacity decreases sharply with charge-discharge cycling. This is possibly due to severe volume changes. The cyclability is improved, however, by employing the copper silicide as a negative electrode. The copper silicide plays an important role as an active material of the electrode, which mitigates volume change cause by the existence of silicon and copper chemical bonding and provides low electrical resistance as well.

• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.553-559
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• 2009

One of zeolitic imidazolate framework materials (ZIF), ZIF-8, has been synthesized with microwave irradiation and conventional electric heating at $140{\sim}180^{\circ}C}$. ZIFs are porous crystalline materials and are similar to metal organic framework (MOF) materials because both ZIFs and MOFs are composed of both organic and metallic components. ZIFs are very stable and similar to zeolites because ZIFs have tetrahedral networks. ZIF-8, with a decreased crystal size, can be synthesized rapidly with microwave irradiation. The microwave synthesis of ZIF-8 is completed in 4 h at $140{^{\circ}C}$ and the reaction time is decreased by about 5 times compared with the conventional electric heating. The ZIF-8 obtained by microwave heating has larger surface area and micropore volume compared with the ZIF-8 synthesized with conventional electric heating. It can be confirmed that ZIF-8s show type-I adsorption isotherms, explaining the microporosity of the ZIF-8s. Based on FTIR and TGA results, it can be understood that the ZIF-8s have similar bonding and thermal characteristics irrespective of heating methods such as microwave and conventional heating.

• Nuclear Engineering and Technology
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• v.13 no.3
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• pp.145-152
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• 1981

Even though a lately reported method of high temperature exchange labelling of o-iodo-hippuric acid (Hippuran) in the absence of oxidizing agent was considered to be an attractive one, the exchange mechanism was somewhat unclear. In this study iodine isotope exchanges between o-iodohippuric acid (OIH) and radioiodide ($^{125}$ $I^{ }$) or between OIH and molecular radioiodine ($^{125}$ $I_2$) were carried out at two different temperatures. Rate constants and activation parameters were measured by applying a radio-paper chromatography technique. Since o-iodobenzoic acid is known as a by-product in the exchange labelling of OIH, data were also obtained for the OIB-iodide systems for comparison. The rate constant was increased in the order of OIB...$^{125}$ $I^{[-10]}$ >OIB...$^{125}$ $I_2$>OIH..$^{125}$ $I^{[-10]}$ >OIH...$^{125}$ $I_2$ and the activation parameters for OIH were generally larger than those for OIB :$\Delta$H$\neq$$_{OIH}$>$\Delta$H$\neq$$_{OIB}$, $\Delta$S$\neq$$_{OIH}$>$\Delta$S$\neq$$_{OIB}$. These results suggest that the mechanism of the high temperature exchange is predominantly nucleophilic even though some electrophilic character can also be involved depending upon reaction conditions. Such a fact may well be caused by a feasible formation of hydrogen bonding type transition state due probably to the ortho substituent effect of-CONHC $H_2$COOH. Thus, the high temperature exchange method is estimated to be quite effective for labelling Hippuran especially at a small research center where reducing agent-free $^{131}$ I is unavailable.ailable..

• Journal of the Society of Cosmetic Scientists of Korea
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• v.43 no.4
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• pp.373-379
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• 2017

We carried out the enzymatic synthesis of 1, 2-hexanediol galactoside (HD-gal) by transgalactosylation reaction using recombinant Escherichia coli ${\beta}-galactosidase$ (${\beta}-gal$). The amounts of ${\beta}-gal$ and 1, 2-hexanediol (HD), pH, and temperature, respectively, were first optimized (${\beta}-Gal$, 4.8 U/mL; HD, 75 mM; pH, 7.0; temperature, $37^{\circ}C$). Under these optimal conditions, about 96% HD was converted to HD-gal. When we investigated the water holding capacities (WHCs) of HD and HD-gal using pig epidermis in the concentrations of 84.4, 126.6, 168.8, 211.0 mM, WHC of HD-gal was superior to HD. In particular, at 168.8 mM HD and HD-gal, WHC of HD-gal showed about 20% greater than that of HD. However, it was observed that MIC values against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus of HD-gal were about three to ten times greater than those of HD, although MIC value of HD-gal against Enterococcus faecalis was almost the same as that of HD. Finally, it was concluded that the covalent bonding of a galactose molecule to HD (transgalactosylation) resulted in an increase in WHC of HD-gal and a decrease in anti-bacterial activity.

• Restorative Dentistry and Endodontics
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• v.23 no.1
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• pp.197-212
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• 1998

The purpose of this study was to evaluate the effects of fluoride application on the aspect of shear bond strength of three aesthetic restorative materials to dentin. One light-cured composite resin(Palfique Esterite) and two light-cured glass ionomer cements(Fuji II LC and Compoglass)were used in this study. 120 permanent molars were used for this study. The teeth were extracted due to the origin of periodontal disease. The crowns of all teeth were removed, and the remaining roots were embedded in epoxy resin. The mesial or distal surfaces of roots were ground flat to expose dentin and polished on wet 320-, 400-, and 600 grit SIC papers for a total of 120 prepared flat root dentin surfaces. The prepared samples were divided into six groups. Group 1, 3, and 5 were control groups and group 2, 4, and 6 were experimental groups. Sixty samples for experimental groups were treated with 2% NaF solution for 5 minutes. Group 1 and 2 were bonded with Plafique Esterite, group 3 and 4 were bonded with Fuji II LC, and group 5 and 6 were bonded with Compoglass. After 24 hours water storage at $37{\pm}1^{\circ}C$, all samples were subjected to a shear to fracture with Instron universal testing machine(No.4467) at 1.0 mm/min displacement rate. Dentin surfaces treated with each conditioners before bonding and interfacial layers between dentin and aesthetic restorative materials were observed under Scanning Electron Microscope(Hitachi S-2300) at 20Kvp. The data were evaluated statistically at the 95% confidence level with ANOVA test. The result were as follows; 1. Among the control groups, group 1 showed strongest bond strength and group 3 showed weakest. 2. Among the experimental groups, group 2 showed strongest bond strength and group 6 showed weakest. 3. Statistical analysis of the data showed that pretreatment of dentin with 2% NaF solution significantly decreased the bond strength of three aesthetic restorative materials to dentin(P<0.05). 4. SEM findings of fluoride treated dentin surfaces (2, 4, 6 group) demonstrated dentin surfaces covered with fluoridated reaction products. 5. Except group 4 and 6, resin tags were formed in all groups.