• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.20 no.4
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• pp.371-382
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• 2022

Carbonates are inorganic ligands that are abundant in natural groundwater. They strongly influence radionuclide mobility by forming strong complexes, thereby increasing solubility and reducing soil absorption rates. We characterized the spectroscopic properties of Am(III)-carbonate species using UV-Vis absorption and time-resolved laser-induced fluorescence spectroscopy. The deconvoluted absorption spectra of aqueous Am(CO₃)₂^- and Am(CO₃)₃^3- species were identified at red-shifted positions with lower molar absorption coefficients compared to the absorption spectrum of aqua Am³⁺. The luminescence spectrum of Am(CO₃)₃^3- was red-shifted from 688 nm for Am³⁺ to 695 nm with enhanced intensity and an extended lifetime. Colloidal Am(III)-carbonate compounds exhibited absorption at approximately 506 nm but had non-luminescent properties. Slow formation of colloidal particles was monitored based on the absorption spectral changes over the sample aging time. The experimental results showed that the solubility of Am(III) in carbonate solutions was higher than the predicted values from the thermodynamic constants in OECD-NEA reviews. These results emphasize the importance of kinetic parameters as well as thermodynamic constants to predict radionuclide migration. The identified spectroscopic properties of Am(III)-carbonate species enable monitoring time-dependent species evolution in addition to determining the thermodynamics of Am(III) in carbonate systems.

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.19-31
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• 2005

During the last decade, the exploration of nanoscale device and circuitry based on molecules has gained increasing interest. In parallel with this, considerable effort is being devoted to the development of molecular photonic/electronic materials based on various porphyrin arrays. This involves light as an input/output signal and excitation energy migration as a mechanism for signal transmission. Absorption of a photon at the light collector end of the porphyrin array yields the excited state, which migrates among the intervening pigments until reaching the emitter, whereupon another photon is emitted. As a consequence, it is relevant to understand the excitation energy transfer (EET) processes occurring in various forms of porphyrin arrays for the applications as artificial light harvesting arrays and molecular photonic/electronic wires. Since the excitonic (dipole) and electronic (conjugation) couplings between the adjacent porphyrin moieties in porphyrin arrays govern the EET processes, we have characterized the EET rates of various forms of multiporphyrin arrays (linear, cyclic, and box) based on various time-resolved spectroscopic measurements. We believe that our observations provide a platform for further development of molecular photonic/electronic materials based on porphyrin arrays.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.390-390
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• 2010

Superconducting proximity effects of Nb/Si(111) were investigated with scanning tunneling microscopy(STM) and scanning tunneling spectroscopy(STS). A highly-doped($0.002\;{\omega}{\diamondsuit}cm$) Si wafer pieces were used as substrate and Nb source was thermally evaporated onto the atomically clean silicon substrate. The temperature of the silicon sample was held at $600^{\circ}C$ during the niobium deposition. And the sample was annealed at $600^{\circ}C$ for 30 minutes additionally. Volmer-Weber growth mode is preferred in Nb/Si(111) at the sample temperature of $600^{\circ}C$. With proper temperature and annealing time, we can obtain Nb islands of lateral size larger than Nb coherence length(~38nm). And outside of the islands, bare Si($7{\times}7$) reconstructed surface is exposed due to the Volmer-Weber Growth mode. STS measurement at 5.6K showed that Nb island have BCS-like superconducting gap of about 2mV around the Fermi level and the critical temperature is calculated to be as low as 6.1K, which is lower than that of bulk niobium, 9.5K. This reduced value of superconducting energy gap indicates suppression of superconductivity in nanostructures. Moreover, the superconducting state is extended out of the Nb island, over to bare Si surface, due to the superconducting proximity effect. Spatially-resolved scanning tunneling spectroscopy(SR-STS) data taken over the inside and outside of the niobium island shows gradually reduced superconducting gap.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.140-145
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• 1992

The excited state intramolecular proton transfer and physical properties of 7-hydroxyquinoline are studied in various solutions and heterogeneous systems by measuring steady state and time-resolved fluorescence, reflection and NMR spectra. Proton transfer is observed only in protic solvents owing to its requirement of hydrogen-bonded solvent bridge for proton relay transfer. The activation energies of the proton transfer are 2.3 and 5.4 kJ/mol in $CH_3OH$ and in $CH_3OD$, respectively. Dimers of normal molecules are stable in microcrystalline powder form and undergo an extremely fast concerted double proton transfer upon absorption of a photon, consequently forming dimers of tautomer molecules. In the supercage of zeolite NaY, its tautomeric form is stable in the ground state and does not show any proton transfer.

• Bulletin of the Korean Chemical Society
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• v.12 no.4
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• pp.429-433
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• 1991

The photoinduced electron transfer reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in various polar solvents were studied by measuring time-resolved fluorescence. The temperature dependence on the fluorescence decay rate in acetonitrile, methanol, ethanol and buthanol was carried out to obtain the activation energy and Arrehnius factor for the photoinduced electron transfer reaction. It was found that as the dielectric constant of the solvent increases, the activation energy and the reaction rate increase. This implys that the Arrehnius factor is important in controlling the photoinduced electron transfer reaction rate. In water, TMPD exists in three forms (cationic, protonated and neutral forms) due to the high dielectric constant and strong proton donating power of water. The photoinduced electron transfer reaction was found to be very fast (< 50 ps) and also the long liverd component in the fluorescence decay profile attributable to the photoexcited protonated form of TMPD was observed. Probably, the reaction pathway and the reaction coordinate seem to be different depending on the solvents studied here.

• Journal of Biomedical Engineering Research
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• v.27 no.2
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• pp.53-58
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• 2006

In this study, transverse relaxation time (T2) measurement and the evaluation of the characteristics of the spectral peak related to stomach tissue metabolites were performed using ex vivo proton magnetic resonance spectroscopic imaging (MRSI) at 1.5-T MRI/S instruments. Thirty-two gastric tissues resected from 12 patients during gastric cancer surgery, of which 19 were normal tissue and 13 were cancerous tissue, were used to measure the $T_2$ of the magnetic resonance spectroscopy (MRS) peaks. The volume of interest data results from the MRSI measurements were extracted from the proper muscle (MUS) layer and the composite mucosa/submucosa (MC/SMC) layer and were statistically analyzed. MR spectra were acquired using the chemical shift imaging (CSI) point resolved spectroscopy (CSI-PRESS) technique with the parameters of pulse repetition time (TR) and echo times (TE) TR/(TE1,TE2)=1500 msec/(35 msec, 144 msec), matrix $size=24{\times}24$, NA=1, and voxel $size=2.2{\times}2.2{\times}4mm^3$. In conclusion, the measured $T_2$ of the metabolite peaks, such as choline (3.21ppm) and lipid (1.33ppm), were significantly decreased (p<0.01 and p<0.05, respectively) in the cancerous stomach tissue.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.762-765
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• 1994

Picosecond time-resolved resonance Raman spectroscopy has been used to study the photochemistry of Cr(CO$)_6$ in cyclohexane following photoexcitation at 266 nm. Photodissociative loss of CO is found to occur within our pulse width of ${\leq}$5 ps by probing the 533 c$m^{-1}$ vibrational mode of ground state Cr(CO$)_6$. The subsequent dynamics after photodissociation are interpreted in terms of solvation, vibrational and electronic relaxations. The vibrational relaxation time of 100 ps and 83 ps are observed by monitoring v=O and v=l of the 381 c$m^{-1}$ transient mode, respectively. No evidence was found for solvation and electronic relaxation occurring on a time scale of ${\leq}$5 ps.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1825-1831
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• 2006

The influence of solvent viscosity on conformational dynamics of the heme-pocket, a small vacant site near the binding site of myoglobin (Mb) and hemoglobin (Hb), and playing a functionally important role by serving as a station in ligand binding and escape, was studied by probing time-resolved vibrational spectra of CO photodissociated from MbCO and HbCO in $D_2O$, 75 wt% glycerol/$D_2O$, and trehalose at 283 K. Two absorption bands ($B_1$ and $B_2$) of the sample in viscous solvents, arising from CO in the heme pocket, are very similar to those in $D_2O$. Two bands in Mb and Hb under all three solvents exhibit very similar nonexponential spectral evolution ($B_1$ band; blue shifting and broadening, $B_2$ band; narrowing with a negligible shifting), suggesting that in the present experimental time window of 100 ps, the extents of the spectral shift and narrowing is much influenced neither by the viscosity of solvent nor by the quaternary contact of Hb. Spectral evolution can be described by a biexponential function with a fast universal time constant of 0.52 ps and a slow time constant ranging from 13 to 32 ps. For both proteins in all three solvents majority of spectral evolution occurs with the fast universal time constant. The magnitude of the slow rate in the spectral shift of B1 band decreases with increasing solvent viscosity, indicating that it is influenced by global conformational change which is retarded in viscous solvent, thereby serve as a reporter of global conformational change of heme proteins after deligation.

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.48 no.6
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• pp.479-487
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• 2020

A new double-pulse laser system that combines Raman and laser induced plasma spectroscopy (LIPS) in a single unit is proposed. The study attempts to enhance the laser induced plasma signals while simultaneously extracting the desired molecular signals from Raman spectroscopy. In low pressure conditions such as the lunar atmosphere, the measuring of plasma emission is hard because of the low electron density and short persistence time causing a rapid plasma expansion. Furthermore, in the integration of the detecting system aimed at space exploration, the minimization of laser system is important in terms of the payload mass. Simultaneous molecular and atomic detection that gave highly resolved spectral data at pressure below 0.07 torr is demonstrated amongst eight rock samples test. The plasma stacking produced from the double-pulse laser enhanced the signal intensity of calcium and oxygen lines in calcite matrix by twofold, compared to a conventional LIPS.

• 한국정보디스플레이학회:학술대회논문집
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• 2003.07a
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• pp.1112-1117
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• 2003

Polarized Fourier transform infrared (IR) absorption is used to probe molecular conformation in a ferroelectric liquid crystal (FLC) during the reorientation induced by the external field. Spectra of planar aligned cells of FLC W314 are measured as functions of IR polarizer orientation and electric field applied to the FLC. The time evolution of the dichroism of the absorbance due to biphenyl core and alkyl tail molecular vibration modes, is observed. Static IR dichroism experiments show a W314 dichroism structure in which the principal axis of dielectric tensor from molecular core vibration are tilted further from the smectic layer normal than those of the tail. This structure indicates the effective binding site in which the molecules are confined in the Sm-C phase has, on average, "zig-zag" shape and this zig-zag binding site structure is rigidly maintained while the molecular axis rotates about the layer normal during field-induced switching.