• Bulletin of the Korean Chemical Society
• /
• v.9 no.3
• /
• pp.117-121
• /
• 1988

The molecular interaction and geometrical optimization of Cr$(CO)_5\;and\;Ni(CO)_3$ units have been studied for phosphinidene complex by means of extended Huckel calculations. The results were compared with those of ab initio calculations and found to be in qualitative agreement. Geometrical optimization of HPCr$(CO)_5\;(1)\;and\;HPNi(CO)_3$ (2) gave the values R = 2.36 ${\AA}$, ${\theta}$ = $111.5^{\circ}$, and ${\phi}$ = $45^{\circ}$for 1, and R = 2.37 ${\AA}$, ${\theta}$= $120^{\circ}$, and ${\phi}$ = $58^{\circ}$for 2. It is found that the low rotational barriers for 1(0.46 kcal $mol^{-1}$) and 2(0.12 kcal $mol^{-1}$) would be accompanied by the free rotation, in spite of the fact that both 1 and 2 adopt staggered conformations.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.10
• /
• pp.1601-1603
• /
• 2006

A novel fluorescent dipyrido[3,2-a:2',3'-c]phenazine (dppz) derivative, 7-(4-methoxybenzoylamino) dppz (1), was synthesized by amide connection to position 7 of the dppz ring. Its fluorescence quantum yield ($\Phi$ = 0.21 in dichloromethane) was as high as that of the conventional 7-amino-dppz (3), and its fluorescence lifetime was much shorter than that of 3.

• Journal of the Semiconductor & Display Technology
• /
• v.21 no.4
• /
• pp.6-13
• /
• 2022

The electrostatic phenomenon seriously issued in extreme ultraviolet semiconductor cleaning was studied in junction with molecular dynamic aspect. It was understood that two lone pairs of electrons in water molecule were subtly different each other in molecular orbital symmetry, existed as two states of large energy difference, and became basis for water clustering through hydron bonds. It was deduced that when hydrogen bond formed by lone pair of higher energy state was broken, two types of [H₂O]⁺ and [H₂O]^- ions would be instantaneously generated, or that lone pair of higher energy state experiencing reactions such as friction with Teflon surface could cause electrostatic generation. It was specifically observed that, in case of electrolyzed cathode water, negative electrostatic charges by electrons were overlapped with negative oxidation reduction potentials without mutual reaction. Therefore, it seemed that negative electrostatic development could be minimized in cathode water by mutual repulsion of electrons and [OH]^- ions, which would be providing excellences on extreme ultraviolet cleaning and electrostatic control as well.

• The Journal of Korean Academy of Prosthodontics
• /
• v.45 no.5
• /
• pp.665-674
• /
• 2007

Purpose: The purpose of this study was to investigate the effect of sire and shape of retention element on the bond strength of indirect composite resin and metal. Material and method: The metal disk specimens, each 6mm in diameter, were cast from CrCo alloy. They were divided into 8 groups by applied retention element. retention bead group $B2\;({\phi}\;0.2mm),\;B4\;({\phi}\;0.4mm),\;B6\;({\phi}\;0.6mm),\;B8\;({\phi}\;0.8mm)$, retention crystal group C2 (0.2mm), C5 (0.5mm), C8 (0.8mm) and sandblasting group SB ($110{\mu}m\;Al_2O_3$ blasting) as control. Eighty-eight metal specimens were veneered with $TESCERA^{(R)}$ Indirect resin system. One specimen of each group was sectioned and the resin-metal bonding pattern at the interface was observed under measuring microscope. Other specimens were then tested for tensile bond strength on an Instron universal testing machine at a crosshead speed of 2mm/min. Results: 1. Compared to sandblasting, beads or crystals increased the resin-metal bond strength (P<.05). 2. 0.2mm retention crystals were most effective in improving the resin-metal bond strength (P>.05). 3. 0.2mm beads showed the highest bond strength among retention bead groups, but there was no statistically significant difference (P>.05). 4. Retention crystals tend to be higher in bond strength than retention beads due to wider surface area. 5. The larger retention element, the larger the undercut for the mechanical retention, but the gap at resin-metal interface was also increased. Conclusion: Within the limitations of this study, 0.2mm retention crystals were most effective in improving the resin-metal bond strength.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.10
• /
• pp.2393-2397
• /
• 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
• /
• v.30 no.1
• /
• pp.214-218
• /
• 2009

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

• The Journal of Korean Academy of Prosthodontics
• /
• v.50 no.2
• /
• pp.112-118
• /
• 2012

Purpose: The purpose of this study was to evaluate the difference in shear bonding strength between resin cements to dental materials when a universal primer (Monobond plus) was applied in place of a conventional primer. Materials and methods: Four groups of testing materials: gold alloy (Argedent Euro, n = 16), non precious metal (T-4, n = 20), zirconia (Cercon, n = 20) and glass ceramic (IPS e.max press, n = 20), were fabricated into discs, which were embedded in an acrylic resin matrix. The gold alloy specimens were airborne-particle abraded, 8 of the specimens were coated with Metal primer II, while the remaining 8 specimens were coated with Monobond plus. The non precious and zirconia specimen were airborne-particle abraded then, the control group received Alloy primer coating, while the other was coated with Monobond plus. Glass ceramic specimens were etched. 10 specimens were coated with Monobond-S and the remaining specimens were coated using Monobond plus. On top of the surface, Multilink N was polymerized in a disc shape. All of the specimens were thermal cycled before the shear bonding strength was measured. Statistical analysis was done with Two sample $t$-test or Mann-Whitney U test (${\alpha}$=.05). Results: There were no significant differences in bonding strength depending on the type of primer used in the gold alloy and glass ceramic groups ($P$>.05), however, the bonding strengths of resin cements to non precious metal and zirconia groups, were significantly higher when the alloy primer was used ($P$<.05). Conclusion: Within the limitations of this study, improvement of universal primers which can be applied to all types of restorations is recommended to precious metals and zirconia ceramics. But, the bond strengths of non precious metals and zirconia ceramics were significantly lower when compared to a 10-MDP primer. More research is needed to apply universal primers to all types of restorations.

• Restorative Dentistry and Endodontics
• /
• v.23 no.1
• /
• pp.487-501
• /
• 1998

In the case of CAD/CAM ceramic inlay restorations, if isthmus width is widened too much, it may cause fracture of remaining tooth structure or loss of bonding at the luting interface because of excessive displacement of buccal or lingual cusps under occlusal loads. So to clarify the criterior of widening isthmus width, this study was designed to test the tensile bond strength and bond failure mode between dentin and ceramic cemented with luting composite resin cements. Cylindrical ceramic blocks(Vita Cerec Mark II, d=4mm) were bonded to buccal dentin of 40 freshly extracted third molars with 4 luting composite resin cements(group1 : Scotchbond Resin Cement/Scotchbond Multi-Purpose, group2 : Duolink Resin Cement/ All-Bond 2, group3: Bistite Resin Cement/Ceramics Primer, and group4:Superbond C&B). Tensile bond test was done under universal testing machine using bonding and measuring alignment blocks(${\phi}ilo$ & Urn, 1992). After immersion of fractured samples into 1 % methylene blue for 24 hours, failure mode was analysed under stereomicroscope and SEM. Results: The tensile bond strength of goup 1, 2 & 4 was $13.97{\pm}2.90$ MPa, $16.49{\pm}3.90$ MPa and $16.l7{\pm}4.32$ MPa, respectively. There was no statistical differences(p>0.05). But, group 3 showed significantly lower bond stregnth($5.98{\pm}1.l7$ MPa, p<0.05). In almost all samples, adhesive fractures between dentin and resin cements were observed. But, in group 1, 2 & 4, as bond strength increased, cohesive fracture within resin cement was observed simultaneously. And, in group 3, as bond strength decreased, cohesive fracture between hybrid layer and composite resin cement was also observed. Cohesive fracture within dentin and porcelain adhesive fracture were not observed. In conclusion, although adhesive cements were used in CAD/CAM -fabricated ceramic inlay restorations, the conservative priciples of cavity preparation must be obligated.

• The Journal of Korean Academy of Prosthodontics
• /
• v.39 no.2
• /
• pp.157-170
• /
• 2001

The bond strength is the most important factor in establishing long-term success of resin-retained fixed prostheses. So, various surface treatment methods have been introduced to improve the bond strength of metal surface and bonding resin till now This study was performed to compare the effect of silicoating with that of metal primer and analyze the correlation between treatment time of sandblasting and the bond strength, so that meant to find more effective surface treatment method that could enhance the bond strength of resin-retained fixed prostheses. The surfaces of all specimens made of $Verabond^{(R)}$ alloys were air abraded with $250{\mu}m\;Al_2O_3$ according to treatment time of sandblasting and they were subdivided to be treated with only sandblasting(S group), silicoating following sandblasting(SS group) and metal primer application after sandblasting(SM group). Then pairs of metal specimens (${\phi}10mm{\times}h\;2mm,\;{\phi}6{\times}h\;2mm$) were bonded with Super bond $C&B^{(R)}$. The specimens were stored in $38^{\circ}C$ water for 48 hours and shear bond strength was measured using the universal testing machine. The results were as follows, 1. In the comparison of shear bond strength according to treatment time of sandblasting, bond strength was increased in the order of 0', 15', 30', 45', 60' group. 0' group had significantly lower value than any other, while 0', 15' group were significantly different with 30', 45', 60' group(p<0.05). 2. In the comparison of shear bond strength according surface treatment methods, bond strength was increased in the order of S group. SS group and SM group. S group was significantly different with SS group and SM group(p<0.05). 3. Observing the mode of bond failure. 0', 15' group showed only adhesive failure, and 30', 45', 60' group did mostly adhesive & cohesive failure in S group. In SS group and SM group, all other groups except 0', 15' group showed mostly cohesive failure. From the above results, it is considered that sandblasting should be treated for more than 30 seconds, and metal primer be more effective and available clinically than silicoater system which is complicate, technique-sensitive and time-consuming method, when nonprecious metal surface is planning be treated with in order enhance the bond strength of resin-retained fixed prostheses.

• Journal of the Korean Chemical Society
• /
• v.33 no.6
• /
• pp.571-576
• /
• 1989

The relativistically parameterized Extended Huckel (REX) calculations are carried out for $[M(NH_3)_5Cl]^{2+}$ (M = Cr, Co, Ru, Rh, Os, Ir). The calculated orbital and overlap populations agree with experimental data. The REX calculations on the electronic structure have been also compared with nonrelativistic EHT results. A ${\phi}$-bonding in M-Cl bond is founded to be more important for the $d^3$, $d^5$complexes than the $d^6$ system.