• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1470-1474
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• 2009

Thermal and photochemistry of methyl iodide ($CH_3I)\;adsorbed\;on\;D_2O$ ice film on Cu(111) at 100 K were studied using temperature-programmed desorption (TPD) time-of-flight mass spectrometry (TOF-MS), X-ray and ultraviolet photoelectron spectroscopies. On the basis of TPD, multilayer and monolayer $CH_3I$ molecules desorb from $D_2O$ ice layer at 120 and 130 K, respectively. Photo-irradiation at 100 K exhibits dramatic changes in the TPD and I $3d_{5/2}\;XPS\;of\;CH_3I$ on ice film, due to a dramatic dissociation of $CH_3I$. The dissociation is likely activated by solvated electrons transferred from the metal substrate during photo-irradiation. No other photo-initiated reaction products were found within our instrumental detection limit. During photo-irradiation, the $CH_3I$, $CH_3$ and I could be trapped (or solvated) in ice film by rearrangement (and self-diffusion) of water molecules. A newly appeared parent molecular desorption peak at 145 K is attributed to trapped $CH_3I$. In addition, the $CH_3$ and I may diffuse through ice and chemisorb on Cu(111), indicated by TPD and I $d_{5/2}$ XPS taken with photo-irradiation time, respectively. No molecular ejection was found during photo-irradiation at 100 K. The work functions for $CH_3I/Cu(111),\;D_2O/Cu(111)\;and\;CH_3I/D_2$O/Cu(111) were all measured to be about 3.9 eV, 1.0 eV downward shift from that of clean Cu(111).

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.107-113
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• 2009

This study investigated the decomposition activities of toluene on 10 mol% Al-W-incorporated mesoporous titano (15 mol %) silicates. The mesopore sizes observed in the transmission electron microscopy images ranged from 2.0 to 5.0 nm, and the pores were irregular on the addition of 10 mol% Al or W ions, but changed to regular hexagonal forms with the simultaneous additions of Al and W. The X-ray photon spectroscopy results showed a shift of the special peak for Ti2p in Al-incorporated mesoporous titanosilicates to a stronger binding energy compared to those of mesoporous titanosilicates and Al-incorporated mesoporous titanosilicates. Three O1s peaks in the spectra of the Al and W coexisted samples were observed at 530.5 and 531.7, 533, and 533.7eV, which were assigned to $Ti-Os\;in\;TiO_2\;and\;Ti_2O_3,\;Si-O\;in\;SiO_2\;and\;Al-O\;in\;Al_2O_3$, respectively. The toluene molecules desorbed at lower temperatures over W-incorporated mesoporous titanosilicates, and the amounts of toluene desorbed were also small; however, Al-incorporated mesoporous titanosilicates adsorbed much more toluene, particular over $Al_7.5-W_2.5-Ti_15-Si_75$. The photocatalytic decomposition of toluene was more enhanced over $Al_7.5-W_2.5-Ti_15-Si_75$ than over Al- or W-incorporated mesoporous titanosilicates only.

• 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.

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.873-881
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• 2009

Bis(phenylethynyl)dimethylsilane is branched by the hydrosilation of the phenylethynyl group with dichloromethylsilane, and then the resulting chlorosilane is reacted with lithium phenylacetylide to give the $1^{st}$ generation. The same hydrosilation and alkynylation are repeated to obtain the $7^{th}$ generation. In addition peripheral Si-Cl moiety of the seven kind generation dendrimers are reacted with alcoholic moiety of 9-hydroxymethylanthracene and 2-(2-hydroxyphenyl)benzoxazole group in the presence of TMEDA. Then three kinds of carbosilane dendrimers are prepared from the $1^{st}$ to the $7^{th}$ generations, the $7^{th}$ generation of each dendrimer has 256 phenylethynyl, 256 9-anthracenylmethoxy, or 128 2-(2-phenoxy)benzoxazole groups. Each synthesized dendrimer is unequivocally characterized by $^1H\;and\;^{13}C\;NMR$, elemental analysis, MALDI-MS, GPC, and PL (photoluminescence). Characteristically PDI (Polydisperse Index) values of the dendrimers’ peak in GPC are in the range of $1.00{\sim}1.07$, which indicates that each generation of carbosilane is in unified distribution. PL spectra of phenylethynyl and 9- anthracenemethoxy group substituted dendrimers show no significant change with increasing the generation from the $1^{st}$ to the $7^{th}$. However, the PL spectra of 2-(2-phenoxy)benzoxazole group substituted dendrimers show a blue-shift trend with increasing the generation from the $1^{st}$ to the $7^{th}$.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2754-2758
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• 2009

Three novel phosphorescent 2-phenylpyridine-based iridium(III) complexes, $[(ppy)_2Ir(P\^{}N)]PF6\;(1),\;[(dfppy)_2Ir(P\^{}N)]PF_6$ (2), and $[(dfmppy)_2 Ir(P\^{}N)]PF6$ (3), where $P\^{}N$ = 2-[(diphenylphosphino)methyl]pyridine (dppmp), were synthesized and characterized. The absorption, photoluminescence, cyclic voltammetry and thermal stability of the complexes were investigated. The complexes showed bright blue luminescences at wavelengths of 448 $\sim$ 500 nm at room temperature in $CHCl_3$ and revealed that the $\pi$-acceptor ability of the phosphorous atom in the ancillary dppmp ligand plays an important role in tuning emission color resulting in a blue-shift emission. The single crystal structure of $[(dfmppy))_2Ir(P\^N)]PF_6$ was determined using X-ray crystallography. The iridium metal center adopts a distorted octahedral structure coordinated to two dfmppy and one dppmp ligand, showing cis C-C and trans N-N chelate dispositions. There is a $\pi-\pi$ overlap between π electrons delocalized in the difluorophenyl rings.

• Journal of the Korean Chemical Society
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• v.17 no.4
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• pp.247-255
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• 1973

The self supported film specimen of Wyoming montmorillonite as a layer silicate saturated by cations,$Li^{+},\;Na^{+},\;K^{+},\;Ca^{2+},\;Ni^{2+},\;Al^{3+}$and$F^{3+}$ were allowed to contact acetone, methyl-ethyl ketone and diethyl ketone within the heatable gas cell. The i.r. spectra between $4000{\sim}1200cm^{-1}$ at different pressures of adsorbates indicated bond formation through carbonyl oxygen. Two types of carbonyl bond shift with maxima at $1713cm^{-1}$ and $1690cm^{-1}$ are attributed as coordinate bond formation of carbonyl with either surface hydroxyl or cationic hydroxyl group. The intensity of the vOH was analyzed and resonance form of cationic hydroxyl was proposed as an adsorption site. The tendency to form coordinate bond was in good agreement with calculated formal charge of carbonyl oxygen in an increasing order, acetone < methyl-ethyl ketone < diethyl ketone. As an additional mechanism of adsorption, weak hydrogen bonding of methyl hydrogen with surface oxygen was observed.

• Membrane Journal
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• v.21 no.4
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• pp.345-350
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• 2011

No investigation has yet been accomplished to screen the boron-doped effects on vanadium based metal membranes. The synthesis, hydrogen permeation properties and chemical stability of a novel Pd-coated $V_{99.8}B_{0.2}$ alloy membrane are presented in this report. Hydrogen permeation experiments have been performed to investigate the hydrogen transport properties through the Pd-coated $V_{99.8}B_{0.2}$ alloy membrane in the absolute pressure range 1.0~3.0 bar under pure hydrogen, hydrogen-carbon dioxide gas mixture at $400^{\circ}C$. The maximum hydrogen permeation flux was $48.5mL/min/cm^2$ for a 0.5 mm thick membrane under pure hydrogen. This results offer new direction in the synthesis of novel non-Palladium-based metal membranes for hydrogen separation in water-gas shift reaction.

• Korean Chemical Engineering Research
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• v.43 no.3
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• pp.360-365
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• 2005

SMB (simulated moving bed) is a continuous chromatographic process by shifting periodically port position. Binary of mixture, Blue dextran and Orange G, was separated by SMB. These components have unique color individually, that is, Blue dextran is blue and Orange G is orange. It is easy to understand SMB process by observing the shift of color changes in SMB. These components was not adsorbed to stationary phase and isolated by difference of size exclusion factor. Mass transfer coefficient was determined by single pulse test under several flow rate conditions. Operation condition was obtained by standing wave theory and optimized for high purities in extract and raffinate streams. Experiment was performed in open loop 4 zone (2-2-2-2) SMB. There are several advantages in open loop SMB, where extract is product for high purity. It is also easy to control flow rate and monitor experimental state during operation. Experimental, extract and raffinate history is well fitted with simulation results, however, column concentration profile is a little different from simulation results. Purities were 99.5％ for extract and 98.9％ for raffinate and extract and raffinate yields were obtained as 98.9％ and 99.4％ respectively.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.10 no.7
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• pp.1661-1667
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• 2009

Post-cure characteristics of a silicone rubber material which is widely used for a LCD lamp holder were investigated using thermogravimetric analysis (TGA). Research was especially focussed on searching for the optimum post-cure conditions in relation to the practical operation environments. The results showed that incipient volatile temperature(Ti) during the process was considered as the most important factor and, thereby, post-curing for 2hrs at $250^{\circ}C$seemed to be a reasonable condition in the practical view-point. Arrhenius plot of shift factors which were empirically determined from the time-temperature-superposition-principle showed good linearity, exhibiting the post-cure mechanism might be proceeded through single mechanism with activation energy of 108.25kJ/mol.

• Bulletin of the Korean Chemical Society
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• v.12 no.2
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.