• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3771-3776
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• 2010

The dynamics of the $CN^-$-ligated ferric cytochrome c (CytcCN) in $D_2O$ at 283 K following Q-band photoexcitation at 575 nm was observed using femtosecond time-resolved vibrational spectroscopy. The equilibrium vibrational spectrum of the CN stretching mode of CytcCN shows two overlapping bands: one main band (82%) at $2122\;cm^{-1}$ with $23\;cm^{-1}$ full width at half maximum (fwhm) and the other band (18%) at $2116\;cm^{-1}$ with $7\;cm^{-1}$ fwhm. The time-resolved spectra show bleaching of the CN fundamental mode of CytcCN and two absorption features at lower energies. The bleach signal and both absorption features are all formed within the time resolution of the experiment (< 200 fs) and decay with a life time of 1.9 ps. One transient absorption feature, appearing immediately red to the bleach signal, results from the thermal excitation of low-frequency modes of the heme that anharmonically couple to the CN fundamental mode, thereby shifting the CN mode to lower energies. The shift of the CN mode decays with a lifetime of 2 ps, equivalent to the time scale for vibrational cooling of the low-frequency heme modes. The other transient absorption feature, which is 3.3 times weaker than the bleach signal and shifted $27\;cm^{-1}$ toward lower energies, is attributed to the CN mode in an electronically excited state where the CN bond is weakened with a lowered extinction coefficient. These observations suggest that photoexcited CytcCN mainly undergoes ultrafast radiationless relaxation, causing photo-deligation of $CN^-$ from CytcCN highly inefficient. As also observed in $CN^-$-ligated myoglobin, inefficient ligand photodissociation might be a general property of $CN^-$-ligated ferric hemes.

• Journal of the Korean Chemical Society
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• v.23 no.1
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• pp.7-14
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• 1979

Changes in CD, ORD and uv-spectra during the mutarotation of poly(trans-5-methyl-L-proline) (PTMP) were studied. The forward mutarotion of PTMP occurred in strong organic acids and trifluoroethanol, while the reverse mutarotation was observed by dilution of the trifluoroethanol solution with excess aliphatic alcohols. The changes in CD, ORD and uv-spectra during the forward and reverse mutarotation proceeded paralell to those found for the mutarotation of polyproline. The chemical shift of the ${\alpha}CH-$proton was shifted downfield about 0.3 ppm during the forward mutarotation. The reduced viscosity for the forward mutarotation increased from 0.15 to 0.26 (dl/g) during 5 days. The equilibrium between form I and form II was estabilished in an appropriate solvent mixture. All changes in solution properties mentioned above are similar to those found for polypoline. These results support that the two forms of PTMP are the same conformations as polyproline form I and form II, i. e., a right-handed helix with all cis amide bonds and a lefthanded helix with all trans amide bonds.

• Korean Journal of Environmental Agriculture
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• v.28 no.3
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• pp.233-237
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• 2009

It has widely been observed that the effect of elevating atmospheric $CO_2$ concentrations on rice productivity depends largely on soil N availabilities. However, the responses of ammonia volatilization from flooded paddy soil that is an important pathway of N loss and thus affecting fertilizer N availability to concomitant increases in atmospheric $CO_2$ and temperature has rarely been studied. In this paper, we first report the interactive effect of elevated $CO_2$ and temperature on ammonia volatilization from rice paddy soils applied with urea. Urea labeled with $^{15}N$ was used to quantitatively estimate the contribution of applied urea-N to total ammonia volatilization. This study was conducted using Temperature Gradient Chambers (TGCs) with two $CO_2$ levels [ambient $CO_2$ (AC), 383 ppmv and elevated $CO_2$ (EC), 645 ppmv] as whole-plot treatment (main treatment) and two temperature levels [ambient temperature (AT), $25.7^{\circ}C$ and elevated temperature (ET), $27.8^{\circ}C$] as split-plot treatments (sub-treatment) with triplicates. Elevated temperature increased ammonia volatilization probably due to a shift of chemical equilibrium toward $NH_3$ production via enhanced hydrolysis of urea to $NH_3$ of which rate is dependent on temperature. Meanwhile, elevated $CO_2$ decreased ammonia volatilization and that could be attributed to increased rhizosphere biomass that assimilates $NH_4^+$ otherwise being lost via volatilization. Such opposite effects of elevated temperature and $CO_2$ resulted in the accumulated amount of ammonia volatilization in the order of ACET>ACAT>ECET>ECAT. The pattern of ammonia volatilization from applied urea-$^{15}N$ as affected by treatments was very similar to that of total ammonia volatilization. Our results suggest that elevated $CO_2$ has the potential to decrease ammonia volatilization from paddy soils applied with urea, but the effect could partially be offset when air temperature rises concomitantly.

• Economic and Environmental Geology
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• v.27 no.4
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• pp.345-361
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• 1994

Lens shaped titanomagnetite ore bodies in the Soyeonpyeong iron mine are embedded in amphibolites, which were intruded into Precambrian metasediments such as garnet-mica schist, marble, mica schist, and quartz schist. Mineral chemistry, K-Ar dating and hydrogen and oxygen stable isotopic analysis for the amphibolites and titanomagnetite ores were conducted to interpret petrogenesis of amphibolite and ore genesis of titanomagnetite iron ore deposits. Amphibolites of igneous origin have unusually high content of $TiO_2$, ranging from 0.94 to 6.39 wt.% with an average value of 4.05 wt.%. REE patterns of the different lithology of the amphibolite show the similar trend with an enrichment of LREE. Amphiboles of amphibolites are consist mainly of calcic amphiboles such as ferro-hornblende, tschermakite, ferroan pargasite, and ferroan pargasitic hornblende. K-Ar ages of hornblende from amphibolite and gneissic amphibolite were determined as $440.04{\pm}6.39Ma$ and $351.03{\pm}5.21Ma$, respectively. This indicates two metamorphic events of Paleozoic age in the Korean peninsula which are correlated with Altin orogeny in China. The titanomagnetite mineralization seems to have occurred before Cambrian age based on occurrence of orebodies and ages of host amphibolites. The Soyeonpyeong iron ores are composed mainly of titanomagnetite, ilmenite, and secondary minerals such as ilmenite and hercynite exsolved in titanomagnetite. The temperature and the oxygen fugacity estimated by the titanomagnetite-ilmenite geothermometer are $500{\sim}600^{\circ}C$ (ave. $550^{\circ}C$) and about $2{\pm}10^{-23}bar$, respectively. Hornblendes from ores and amphibolites which responsible for magnetite ore mineralization, have a relatively homogeneous isotopic composition ranging from +0.8 to +3.9 ‰ in ${\delta}^{18}O$ and from -87.8 to -113.3 ‰ in ${\delta}D$. The calculated oxygen and hydrogen isotopic compositions of the fluids which were in equilibrium with hornblende at $550^{\circ}C$, range from 2.8 to 5.9‰ in ${\delta}^{18}O_{H2O}$ and from -60.41 to -81.31 ‰ in ${\delta}D_{H2O}$. The ${\delta}^{18}O_{H2O}$ value of magnetite ore fluids are in between +6.4 to + 7.9 ‰. All of these values fall in the range of primary magmatic water. A slight oxygen shift means that $^{18}O$-depleted meteoric water be acted with basic fluids during immiscible processes between silicate and titaniferous oxide melt. Mineral chemistry, isotopic compositions, and occurences of amphibolites and orebodies, suggest that the titanomagnetite melt be separated immisciblely from the titaniferous basic magma.

• Journal of the Korean Chemical Society
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• v.33 no.3
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• pp.273-280
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• 1989

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.

• Economic and Environmental Geology
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• v.28 no.2
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• pp.109-121
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• 1995

The hydrothermal vein type deposits which comprise the Kasihan, Jompong and Gempol mineralized areas are primarily copper and zinc deposits, but they are also associated with lead and/or gold mineralization. The deposits occur within the Tertiary sedimentary and volcanic rocks in the Southern Mountain zone of the eastern Java island, Indonesia. Mineralization can be separated into two or three distinct stages (pre-and/or post- ore mineralization stages and main ore mineralization stage) which took place mainly along pre-existing fault breccia zones. The main phase of mineralization (the main ore stage) can be usually classified into three substages (early, middle and late) according to ore mineral assemblages, paragenesis, textures and their chemical compositions. Ore mineralogy and paragenesis of the three areas in the district are different from each other. Pyrite, pyrrhotite (/arsenopyrite), iron-rich (up to 20.5 mole % FeS) sphalerite and (Cu-)Pb-Bi sulfosalts are characteristic of the deposits in the Kasihan (/Jompong) area. On the other hand, pyrite + hematite + magnetite + iron-poor (2.7 to 3.6 mole % FeS) sphalerite assemblage is restricted to the Gempol area. Fluid inclusion data suggest that fluids of the main ore stage evolved from initial high temperatures (near $350^{\circ}C$) to later lower temperatures (near $200^{\circ}C$) with salinities ranging from 0.8 to 10.1 equiv. wt. percent NaCl. Each area represents a separate hydrothermal system: the mineralization at Kasihan and Jompong were largely due to early fluid boiling coupled with later cooling and dilution, whereas the mineralization at Gempol was mainly resulted from cooling and dilution by an influx of cooler meteoric waters. Fluid inclusion evidence of boiling indicates that pressures of ${\geq}95$ to 255 bars (${\geq}95$ bars for the Gempol area: $\approx$ 120 to 170 bars for the Jompong area: $\approx$ 140 to 255 bars for the Kasihan area) during portions of main ore stage mineralization. Equilibrium thermodynamic interpretation indicates that the evolution trends of the temperature versus fS2 variation of ore stage fluids in the Pacitan district follow two fashions: ore fluids at Kasihan and Jompong changed from the pyrite-pyrrhotite sulfidation stage towards pyritehematite- magnetite state, whereas those at Gempol evolved nearly along pyrite-hematite-magnetite reaction curve with decreasing temperature. The sulfur isotope compositions of sulfide minerals are consistent with an igneous source of sulfur with a ${\delta}^{34}S_{{\Sigma}s}$ value of about 3.3 per mil. The oxygen and hydrogen isotopic compositions of the fluids in each area indicate a progressive shift from the dominance of highly exchanged meteoric water at early hydrothermal systems towards an un- or less-exchanged meteoric water at later hydrothermal systems.

• Strategy21
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• s.38
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• pp.112-162
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• 2015

This study began to confirm or review the balance of power theory by applying scientific methods through experiential cases. Though there are several kinds of national power, this study supposes military power as a crucial power when it comes to war and peace. This research covered balance and imbalance through comparing relative military power between nations or nations' group. Comparison of relative military power can be achieved by statistically processing the values of which has been converted into the standard variables in same domain, then calculating the values of nation's power which has been synthesized different experiential factors. In addition, the criteria of experiential experiment is highly dedicated to European countries, USA, Japan prior to 1st and 2nd World War, as well as USA, Soviet Union and North East Asia during Cold War era. In addition, the balance of power theory has been redefined to review the action of the state upon the changes of power as mentioned in the theory. To begin with, the redefined theory states that relative level of military power between nations defines the consistency of peace and balance of power. If military power is enough to be on the range of level required to keep the power in equilibrium, peace and balance can be achieved. The opposite would unbalance the military power, causing conflicts. While the relative military level between nations change, nations seek to establish 'nations group' via military cooperation such as alliance, which also shift relative military power between nations group as well. Thus, in order to achieve balance of power, a nation seeks to strengthen its military power(self-help), while pursuing military cooperation(or alliance). This changes relative military power between nations group also. In other words, if there exists balance of power between nations, there is balance of power between nations group as well. In this theory, WWI and II broke out due to the imbalance of military force between nations and nations group, and reviewed that due to the balance of military force during the Cold War, peace was maintained. WWI was resulted from imbalance of military cooperation between two powerful states group and WWII was occurred because of the imbalance among the states. Peace was maintained from cooperation of military power and balance among the states during the Cold War. Imbalance among continental states is more threatening than maritime states and balance of power made by army force and naval force also is feasible. Also the outcomes of two variables are found military power balanced ratio of military power for balance is 67% when variable ratio of balance is 100% and standard value for balance is 0.86. Military power exists in a form of range. The range is what unstabilized the international system causing nations to supplement their military powers. These results made possible the calculation and comparison between state's military power. How balance of power inflicted war and peace has been studied through scientific reviews. Military conflict is highly possible upon already unbalanced military powers of North East Asian countries, if the US draws its power back to America. China and Japan are constantly building up their military force. On the other hand, Korean military force is inferior so in accordance to change of international situation state's survival could be threatened and it is difficult to achieve drastic increase in military force like Germany did. Especially constructing naval force demands lots of time; however but has benefit that naval force can overcome imbalance between continental states and maritime states.

• Economic and Environmental Geology
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• v.25 no.4
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• pp.417-433
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• 1992

Lead-zinc-copper deposits of the Jeonheung and the Oksan mines around Euiseong area occur as hydrothermal quartz and calcite veins that crosscut Cretaceous sedimentary rocks of the Gyeongsang Basin. The mineralization occurred in three distinct stages (I, II, and III): (I) quartz-sulfides-sulfosalts-hematite mineralization stage; (II) barren quartz-fluorite stage; and (III) barren calcite stage. Stage I ore minerals comprise pyrite, chalcopyrite, sphalerite, galena and Pb-Ag-Bi-Sb sulfosalts. Mineralogies of the two mines are different, and arsenopyrite, pyrrhotite, tetrahedrite and iron-rich (up to 21 mole % FeS) sphalerite are restricted to the Oksan mine. A K-Ar radiometric dating for sericite indicates that the Pb-Zn-Cu deposits of the Euiseong area were formed during late Cretaceous age ($62.3{\pm}2.8Ma$), likely associated with a subvolcanic activity related to the volcanic complex in the nearby Geumseongsan Caldera and the ubiquitous felsite dykes. Stage I mineralization occurred at temperatures between > $380^{\circ}C$ and $240^{\circ}C$ from fluids with salinities between 6.3 and 0.7 equiv. wt. % NaCl. The chalcopyrite deposition occurred mostly at higher temperatures of > $300^{\circ}C$. Fluid inclusion data indicate that the Pb-Zn-Cu ore mineralization resulted from a complex history of boiling, cooling and dilution of ore fluids. The mineralization at Jeonheung resulted mainly from cooling and dilution by an influx of cooler meteoric waters, whereas the mineralization at Oksan was largely due to fluid boiling. Evidence of fluid boiling suggests that pressures decreased from about 210 bars to 80 bars. This corresponds to a depth of about 900 m in a hydrothermal system that changed from lithostatic (closed) toward hydrostatic (open) conditions. Sulfur isotope compositions of sulfide minerals (${\delta}^{34}S=2.9{\sim}9.6$ per mil) indicate that the ${\delta}^{34}S_{{\Sigma}S}$ value of ore fluids was ${\approx}8.6$ per mil. This ${\delta}^{34}S_{{\Sigma}S}$ value is likely consistent with an igneous sulfur mixed with sulfates (?) in surrounding sedimentary rocks. Measured and calculated hydrogen and oxygen isotope values of ore-forming fluids suggest meteoric water dominance, approaching unexchanged meteoric water values. Equilibrium thermodynamic interpretation indicates that the temperature versus $fs_2$ variation of stage I ore fluids differed between the two mines as follows: the $fs_2$ of ore fluids at Jeonheung changed with decreasing temperature constantly near the pyrite-hematite-magnetite sulfidation curve, whereas those at Oksan changed from the pyrite-pyrrhotite sulfidation state towards the pyrite-hematite-magnetite state. The shift in minerals precipitated during stage I also reflects a concomitant $fo_2$ increase, probably due to mixing of ore fluids with cooler, more oxidizing meteoric waters. Thermodynamic consideration of copper solubility suggests that the ore-forming fluids cooled through boiling at Oksan and mixing with less-evolved meteoric waters at Jeonheung, and that this cooling was the main cause of copper deposition through destabilization of copper chloride complexes.