• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3590-3594
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• 2014

Blue phosphorescent $(dfpypy)_2Ir(mppy)$, where dfpypy = 2',6'-difluoro-2,3'-bipyridine and mppy = 5-methyl-2-phenylpyridine, has been synthesized by newly developed effective method and its solid state structure and photoluminescent properties are investigated. The glass-transition and decomposition temperature of the compound appear at $160^{\circ}C$ and $360^{\circ}C$, respectively. In a crystal packing structure, there are two kinds of intermolecular interactions such as hydrogen bonding ($C-H{\cdots}F$) and edge-to-face $C-H{\cdots}{\pi}(py)$ interaction. This compound emits bright blue phosphorescence with ${\lambda}_{max}=472nm$ and quantum efficiencies of 0.23 and 0.32 in fluid and the solid state. The emission band of the compound is red-shifted by 40 nm relative to homoleptic congener, $Ir(dfpypy)_3$. The ancillary ligand in $(dfpypy)_2Ir(mppy)$ has been found to significantly destabilize HOMO energy, compared to $Ir(dfpypy)_3$, $(dfpypy)_2Ir(acac)$ and $(dfpypy)_2Ir(dpm)$, without significantly changing LUMO energy.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2448-2452
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Membrane Journal
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• v.5 no.2
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• pp.89-96
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• 1995

The monolayer characteristics of phosphate amphiphiles with azobenzene at air/water interface were studied by the measurment of $\pi-A$ curves and absorption spectra. Immediately after being spread on the water surface, these amphiphiles having strong intermolecular hydrogen bonding interactions showed the typical absorption spectra which resulted from domain formation. But the aggregated domains could be controlled by changing the subphase conditions (adding bulky salt and rasing pH). Addition of metal ions in subphase changes the molecular orientation of monolayer. As the metal ion charge increases ($1\leq2$ < 3 < 4 valence), the absorption maximum (310nm) of the amphiphile with azobenzene shifts to a longer wavelength (350nm) which means that the orientation of the amphiphile is tilted. These results suggest that the molecular orientation, and furthermore the aggregation state of monolayer can be possibly controlled by the interaction of metal ions with different charge types.

• Journal of Photoscience
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• v.9 no.2
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• pp.311-313
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• 2002

X-ray structures of pharaonis phoborhodopsin (ppR) show the different direction of the side chain of Arg72 from that of the corresponding residue (Arg82) of bacteriorhodopsin, BR. For BR, this residue is considered to play an important role in the proton pumping. In order to investigate the role of Arg72 in ppR, we constructed Arg72 mutants of R72A, R72K and R72Q, and measured the photocycle and proton pumping activities. The pH-titration curves on the absorption maximum of the mutants were shifted to alkaline in comparison of that of the wild-type. This may imply the increase of pKa of D75, suggesting the presence of the (probably electric) interaction between D75 and Arg72. Rate constants of the M-decay were 3-7 times faster than that of the wild-type, and the time for the completion of the photocycling was also reduced. Using Sn0$_2$ electrode, the rate of transmembrane proton transport was measured upon illumination. The photo-induced proton pumping activities were estimated after the corrections that are the percentages of the associated form of D75 (which has no pumping activity) and the photocycling rates. R72A and R72Q showed the reduced activity while R72K did not reduce the activity.

• The Journal of Advanced Prosthodontics
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• v.4 no.2
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• pp.103-108
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• 2012

PURPOSE. Debonding of a composite resin core of the fiber post often occurs at the interface between these two materials. The aim of this study was to evaluate the effects of different surface treatment methods on bond strength between fiber posts and composite core. MATERIALS AND METHODS. Sixty-four fiber posts were picked in two groups (Hetco and Exacto). Each group was further divided into four subgroups using different surface treatments: 1) silanization; 2) sandblasting; 3) Treatment with 24% $H_2O_2$, and 4) no treatment (control group). A cylindrical plexiglass matrix was placed around the post and filled with the core resin composite. Specimens were stored in 5000 thermal cycles between $5^{\circ}C$ and $55^{\circ}C$. Tensile bond strength (TBS) test and evaluation using stereomicroscope were performed on the specimen and the data were analyzed using two-way ANOVA, Post Hoc Scheffe tests and Fisher's Exact Test (${\alpha}$=.05). RESULTS. There was a significant difference between the effect of different surface treatments on TBS ($P$ <.001) but different brands of post ($P$=.743) and interaction between the brand of post and surface treatment ($P$=.922) had no significant effect on TBS. Both silanization and sandblasting improved the bonding strength of fiber posts to composite resin core, but there were not any significant differences between these groups and control group. CONCLUSION. There was not any significant difference between two brands of fiber posts that had been used in this study. Although silanization and sandblasting can improve the TBS, there was not any significant differences between surface treatments used.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1315-1327
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• 2002

The model compounds, 8-methoxypsoralen-CH2O(CH2)n-adenine (MOPCH2OCnAd, n=2, 3, 5, 6, 8, and 10) in which 5 position of 8-methoxypsoralen (8-MOP) is linked by various lengths of polymethylene bridge to N9 of adenine. UV absorption spectra are identical with the sum of MOPCH2OC3 and adenine absorption spectra. Solvent effects on the UV absorption and fluorescence emission spectra indicate that the lowest excited singlet state is the $(\pi${\rightarrow}$\pi*)$ state. The spectral characteristics of the fluorescence of MOPCH2OCnAd are strongly dependent upon the nature of the solvents. The fluorescence emission spectra in aprotic solvents are broad and structureless due to the excimer formation through the folded conformation accelerated by hydrophobic ${\pi}-{\pi}$ stacking interaction. Increasing polarity of the protic solvents leads to higher population of unfolded conformation stabilized through favorable solvation and H-bonding, and consequently to an increase in the fluorescence intensity, fluorescence lifetime, and a shift of fluorescence maximum to longer wavelengths. The decay characteristics of the fluorescence in polar protic solvents shows two exponential decays with the lifetimes of 0.6-0.8 and 1.6-1.9 ns in 5% ethanol/water, while MOPCH2OC3 shows 0.5 and 1.7 ns fluorescence lifetimes. The long-lived component of fluorescence can be attributed to the relaxed species (i.e., the species for which the solvent reorientation (or relaxation) has occurred), while the short-lived components can be associated with the unrelaxed, or only partially relaxed, species.

• Applied Microscopy
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• v.31 no.2
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• pp.117-128
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• 2001

DMF is not a good solvent for PVA. There is no solvent-PVA interaction such as H-bonding. DMF/PVA makes a UCST system. DMF/PVA makes a gel through crystallization-induced gelation. X-ray, thermal analysis, and other experimental proofs are presented. The gelation rate was faster at low temperature. Small addition of PEG increased the rate of gelation, but urea decreased the rate. SEM showed the phase demixing process very clearly. In the early stage of gelation, only phase demixing was occurring at a low rate. Hence, no holes appear in the early stage photographs. As demixing proceeded further, the holes began to appear and the sizes became bigger. DMF phase remains many holes after vaporization and PVA phase constitute the matrix phase.

• Journal of the Korean Chemical Society
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• v.31 no.1
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• pp.3-13
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• 1987

Infrared absorption spectra of alkyl alcohols in the OH stretching region were obtained from varying the concentrations of alcohols in $CCl_4$. The OH stretching bands were broadened and shifted to lower frequencies due to the hydrogen-bond formation. Three bands were obtained from the breakdown of these bands by the simplex method. Each band was assigned to various types of hydrogen-bonded OH groups. The electronic structures and interaction energies of dimeric and trimeric alcohols were calculated by semi-empirical MO(CNDO/2, INDO) methods. These results were in good agreement with those of deconvoluted ir spectra. The EDA(electron donor-acceptor) effect of alkyl group on hydrogen-bond formation was in the decreasing order of butyl > propyl > ethyl > methyl group. On the other hand, the experimental results were in the order : propyl > ethyl > butyl > methyl group. This seemed to be ascribed to the bulkiness of butyl alcohol.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1946-1952
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• 2005

New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.