• The Journal of Korean Academy of Prosthodontics
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• v.30 no.2
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• pp.135-154
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• 1992

This study was performed to analyze bond strength, the alterations of the interfaces between metal films which are populary used and considered to contribute to the chemical reaction with porcelain, according to constant ion- beam- mixing, and the relation between interfacial chemical reactions and bond strength in metal/porcelain specimens. For this study, three seperate metals : selected-gold, indium and tin were chosen ; each to be bonded to a seperate body porcelain. Bonding occurs when the metal is deposited to the body porcelain using a vacuum evaporator. The vacuum evaporator used $10^{-5}\sim10^{-6}$ Torr vacuum states for the evaporation of various metals (Au, Sn, In). Ion-beam-mixing of the porcelain/metal interfaces caused reactions when the Ar+ was implanted into thin films using a 80 KeV accelerator. These ion-beam-mixed specimens were then compared with an unmixed control group. An analysis of bond strength and ionic changes between the the metal and porcelain was performed by electron spectroscopy of chemical analysis (ESCA) and scratch test. The finding led to the following conclusions : 1. Light microscopic views of the scratch test : The ion-beam-mixed Au/porcelain specimen showed narrower scratched streams than the unmixed specimen. However, the Sn/porcelain, In/porcelain specimens showed no differences in the two conditions. 2. Acoustic emissions in scratch tests : The ion-mixed Au/porcelain, In/porcelain specimens showed signals closer to the metal/porcelain interfaces than unmixed specimens. Conversely, the ion-mixed Sn/porcelain specimen showed more critical signals in superficial portions than unmixed specimens. 3. After ion- beam-mixing, the Au/porcelain specimen showed apparently increased bond strength, and the In/porcelain specimen showed very slightly increased bond strength. However, the Sn/porcelain specimen showed no differences between ion mixed specimen and the unmixed one. 4. ESCA analysis : The ion-beam-mixed Au/porcelain specimen showed a higher peak separated value (4.3eV) than that of the unmixed specimen(3.65eV), the ion-beam-mixed In/porcelain specimen showed a higher peak separated value (9.43eV) than that of the unmixed specimen(7.6eV) and the ion-beam-mixed Sn/porcelain specimen showed a higher peak separated value (8.79eV) than that of the unmixed specimen(8.5eV). 5. Interfacial changes were observed in the ion-mixed Au/porcelain, In/porcelain and Sn/porcelain specimens. Especially, significant interfacial changes were measured in the ion- mixed Sn/porcelain specimen. Tin dioxide(SnO2) and a combination of pure tin and tin dioxide (Sn+SnO2) were produced. 6. In the Au/porcelain specimen, the interfacial chemical reaction showed increased bond strength between gold and porcelain substrate. But, in the In/porcelain, Sn/porcelain specimens, interfacial chemical reactions did not affected the bond strength between metal and porcelain substrate. Especially, bonding strength on the ion mixed Sn/porcelain specimen showed the least amount of difference.

• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• Restorative Dentistry and Endodontics
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• v.35 no.5
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• pp.321-334
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• 2010

Objectives: The purpose of this study is to evaluate bonding efficacy by means of measuring the effect of remained solvent on Degree of conversion(DC) and ${\mu}TBS$ and FE-SEM examination. Materials and Methods: Two 2-step total etching adhesives and two single-step self etching adhesives were used in this study. First, volume weight loss of 4 dentin adhesives were measured using weighting machine in process of time in normal conditions and calculate degree of evaporation (DE). Reaction/reference intensity ratio were measured using micro-Raman spectroscopy and calculate DC according to DE. Then 2 experimental groups were prepared according to air-drying methods (under, over) and control group was prepared to manufacturer's instruction. Total 12 groups were evaluated by means of micro tensile bond strength and FE-SEM examination. Results: Degree of evaporation (DE) was increased as time elapsed but different features were observed according to the kind of solvents. Acetone based adhesive showed higher DE than ethanol and butanol based adhesive. Degree of conversion (DC) was increased according to DE except for $S^3$ bond. In ${\mu}TBS$ evaluation, bond strength was increased by additional air-drying. Large gaps and droplets were observed in acetone based adhesives by FE-SEM pictures. Conclusions: Additional air-drying is recommended for single-step self etching adhesive but careful consideration is required for 2-step total etching adhesive because of oxygen inhibition layer. Evaporation method is carefully chose and applied according to the solvent type.

• Biotechnology and Bioprocess Engineering:BBE
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• v.9 no.2
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• pp.132-136
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• 2004

The LAL (Limulus amebocyte lysate) test for the detection and quantification of endotoxin is based on the gelation reaction between endotoxin and LAL from a blood extract of Limulus polyphemus. The test is labor intensive, requiring dedicated personnel, a relatively long reaction time (approximately 1 h), relatively large volumes of samples and reagents and the detection of the end-point is rather subjective. To solve these problems, a miniaturized LOC (lab-on-a-chip) prototype, 62mm (L) ${\times}$ 18 mm (W), was fabricated using PDMS (polydimethylsiloxane) bonded to glass. Using this prototype, in which 2mm (W) ${\times}$ 44.3mm (L) ${\times}$ 100 $\mu\textrm{m}$ (D) microfluidic channel was constructed, turbidometric and chromogenic assay detection methods were compared, and the chromogenic method was found the most suitable for a small volume assay. In this assay, the kinetic-point method was more accurate than the end-point method. The PDMS chip thickness was found to be minimized to around 2 mm to allow sufficient light transmittance, which necessitated the use of a glass slide bonding for chip rigidity. Due to this miniaturization, the test time was reduced from 1 h to less than 10 min, and the sample volume could be reduced from 100 to ca. 4.4 ${\mu}$L. In summation, this study suggested that the LOC using the LAL test principle could be an alternative as a semi-automated and reliable method for the detection of endotoxin.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1491-1504
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• 2012

InP quantum dot (QD)-organosilicon nanocomposites were synthesized and their photoluminescence quenching was mainly investigated because of their applicability to white LEDs (light emitting diodes). The as-synthesized InP QDs are capped with myristic acid (MA), which are incompatible with typical silicone encapsulants. We have introduced a new ligand, 3-aminopropyldimethylsilane (APDMS), which enables embedding the QDs into vinyl-functionalized silicones through direct chemical bonding. The exchange of ligand from MA to APDMS does not significantly affect the UV absorbance of the InP QDs, but quenches the PL to about 10% of its original value with the relative increase in surface related emission intensities, which is explained by stronger coordination of the APDMS ligands to the surface indium atoms. InP QD-organosilicon nanocomposites were synthesized by connecting the QDs using a short cross-linker such as 1,4-divinyltetramethylsilylethane (DVMSE) by the hydrosilylation reaction. The formation and changes in the optical properties of the InP QD-organosilicon nanocomposite were monitored by ultraviolet visible (UV-vis) absorbance and steady state photoluminescence (PL) spectroscopies. As the hydrosilylation reaction proceeds, the QD-organosilicon nanocomposite is formed and grows in size, causing an increase in the UV-vis absorbance due to the scattering effect. At the same time, the PL spectrum is red-shifted and, very interestingly, the PL is quenched gradually. Three PL quenching mechanisms are regarded as strong candidates for the PL quenching of the QD nanocomposites, namely the scattering effect, F$\ddot{o}$rster resonance energy transfer (FRET) and cross-linker tension preventing the QD's surface relaxation.

• Molecules and Cells
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• v.41 no.4
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• pp.331-341
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• 2018

L-pipecolic acid is a non-protein amino acid commonly found in plants, animals, and microorganisms. It is a well-known precursor to numerous microbial secondary metabolites and pharmaceuticals, including anticancer agents, immunosuppressants, and several antibiotics. Lysine cyclodeaminase (LCD) catalyzes ${\beta}$-deamination of L-lysine into L-pipecolic acid using ${\beta}$-nicotinamide adenine dinucleotide as a cofactor. Expression of a human homolog of LCD, ${\mu}$-crystallin, is elevated in prostate cancer patients. To understand the structural features and catalytic mechanisms of LCD, we determined the crystal structures of Streptomyces pristinaespiralis LCD (SpLCD) in (i) a binary complex with $NAD^+$, (ii) a ternary complex with $NAD^+$ and L-pipecolic acid, (iii) a ternary complex with $NAD^+$ and L-proline, and (iv) a ternary complex with $NAD^+$ and L-2,4-diamino butyric acid. The overall structure of SpLCD was similar to that of ornithine cyclodeaminase from Pseudomonas putida. In addition, SpLCD recognized L-lysine, L-ornithine, and L-2,4-diamino butyric acid despite differences in the active site, including differences in hydrogen bonding by Asp236, which corresponds with Asp228 from Pseudomonas putida ornithine cyclodeaminase. The substrate binding pocket of SpLCD allowed substrates smaller than lysine to bind, thus enabling binding to ornithine and L-2,4-diamino butyric acid. Our structural and biochemical data facilitate a detailed understanding of substrate and product recognition, thus providing evidence for a reaction mechanism for SpLCD. The proposed mechanism is unusual in that $NAD^+$ is initially converted into NADH and then reverted back into $NAD^+$ at a late stage of the reaction.

• Textile Coloration and Finishing
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• v.1 no.1
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• pp.7-18
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• 1989

The distinguishing characteristic of the glow discharge is that chemical reaction induced by partially ionized gases are limited only to the substrate surface. Most studies have been done on the plasma etching and polymerization. The graft polymerization in vapour phase by cold plasma has been rarely investigated. In this study the system of tub3ar reaction chamber with capacitively coupled electrode of alternative current of 60 Hz was employed for the graft polymerization. The graft polymerization of Acylic Acid(AA) onto the poly (ethylene terephthalate) (PET) was carried out by treatment of PET film and fabric by cold plasma (glow discharge of argon gas), followed by the supply of AA vapour. The graft yield was about 1 wt%. The surface property was determined by contact angle, the surface tension was evaluated by zisman’s plot and equation of surface tension mesurement. The results were as follows: 1. In order to obtain lower contact angle, it was effective to avoid the vicinity of electrodes for a setting position of substrate. 2. Contact angle affected on the monomer pressure and its duration of exposure to the acid vapour. 3. Polymer radical formation was influenced by the changes of the value of current density and plasma treatment time. 4. Total surface tension of plasma grafted PET film increased. With an increase in the carboxylic acid content, the dispersion force decreased, while, the polar force and hydrogen bonding force increased. 5. The contact angle decreased from $75^\circ$ to around $30^\circ$ by plasma grafting. There was no ageing effect on the contact angle after 4 months.

• Archives of Pharmacal Research
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• v.24 no.5
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• pp.455-465
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• 2001

The highly potent cytotoxic DNA-DNA cross-linker consists of two cyclopropa[c]pyrrolo[3,4-3]indol-4(5H)-ones insoles [(+)-CPI-I] joined by a bisamido pyrrole (abbreviated to "Pyrrole"). The Pyrrole is a synthetic analog of Bizelesin, which is currently in phase II clinical trials due to its excellent in vivo antitumor activity. The Pyrrole has 10 times more potent cytotoxicity than Bizelesin and mostly form DNA-DNA interstrand cross-links through the N3 of adenines spaced 7 bp apart. The Pyrrole requires a centrally positioned GC base pair for high cross-linking reactivity (i.e., $5^1$-T$AT_2$A*-$3^1$), while Bizelesin prefers purely AT-rich sequences (i.e., $5^1$-T$AT_4$A*-$3^1$, where /(equation omitted) represents the cross-strand adenine alkylation and A* represents an adenine alkylation) (Park et al., 1996). In this study, the high-field $^1$H-NMR and rMD studies are conducted on the 1 1-mer DNA duplex adduct of the Pyrrole where the 5′(equation omitted)TAGTTA*-3′sequence is cross-linked by the drug. A severe structural perturbation is observed in the intervening sequences of cross-linking site, while a normal B-DNA structure is maintained in the region next to the drug-modified adenines. Based upon these observations, we propose that the interplay between the bisamido pyrrole unit of the drug and central C/C base pair (hydrogen-bonding interactions) is involved in the process of cross-linking reaction, and sequence specificity is the outcome of those interactions. This study suggests a mechanism for the sequence specific cross-linking reaction of the Pyrrole, and provides a further insight to develop new DNA sequence selective and distortive cross-linking agents.

• Journal of the Microelectronics and Packaging Society
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• v.11 no.4 s.33
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• pp.1-5
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• 2004

A multi-layer flexible substrate is composed of copper(Cu)/polyimide that are known as good electrical conductivity, and low dielectric constant, respectively. In this study. conductor line of $5{\mu}m$-pitch was successfully fabricated without non-uniform pattern shape by electroplating copper and coating polyimide on patterned stainless steel. For multi-layer flexible substrate, via holes were drilled by UV laser and filled with electroplating copper and tin. And then, the PI layer with vias and conductor lines was stripped from stainless steel substrate. The PI layers were laminated at once with careful alignment between layers. Solid state reaction between tin and copper during lamination formed the intermetallic compounds of $Cu_6Sn_5$($\eta$-phase) and $Cu_3Sn$($\epsilon$-Phase) and achieved a complete inter-connection by vertically positioning the plugged via holes on via pad. The via formation process has several advantages; such as better electrical property and lower cost than V type via and paste via.

• KSBB Journal
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• v.18 no.5
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• pp.429-433
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• 2003

LAL (Limulus amebocyte lysate) test to detect and quantity endotoxin is based on gellation reaction between endotoxin and LAL from a blood extract of Limulus polyphemus. The test is labor intensive requiring dedicated personnel, takes relatively long reaction time (approximately 1 hr), requires relatively large volume of samples and reagents, and its end-point detection method is rather subjective. To solve these problems, we attempted to develop a miniaturized LOC (lab-on-a-chip) prototype using PDMS and glass. Using the 62 mm (length) ${\times}$ 18 mm (width) prototype in which 2 mm (width) ${\times}$ 44.34 mm (length) ${\times}$ 100 $\mu\textrm{m}$ (depth) microfluidic channel was provided, we compared the various detection methods of gellation, turbidometric, and chromogenic assays to find the chromogenic method to be the most suitable for small volume assay. In this assay, kinetic point method was more accurate than end point method. We also found the PDMS chip thickness should be minimized to around 2 mm to allow sufficient light transmittance, which necessitated a glass slide bonding for chip rigidity. Through the miniaturization, the test time was reduced from 1 hr to less than 10 minutes, and the sample volume could be reduced from 100 ${\mu}\ell$ to 4.4 ${\mu}\ell$. In sum, this study revealed that the mini LOC could be an alternative for a semi-automated and reliable method for LAL test.