• Bulletin of the Korean Chemical Society
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• 제23권2호
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• pp.267-270
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• 2002

Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of $C_7H_7^+$ products were determined by examining their bimolecular reactivities toward toluene-$d_8$. The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of $C_7H_7^+$ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzyl cation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta >0.09 for ortho >0.05 for para.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2343-2353
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• 2007

We report the application of time-dependent density functional theory (TDDFT) to the calculation of potential energy profile relevant to the excited state intramolecular proton transfer (ESIPT) processes in title molecules. The TDDFT single point energy calculations along the reaction path have been performed using the CIS optimized structure in the excited state. In addition to the Stokes shifts, the transition energies including absorption, fluorescence, and 0-0 transition are estimated from the TDDFT potential energy profiles along the proton transfer coordinate. The excited state TDDFT potential energy profile of SA and 3ASA resulted in very flat function of the OH distance in the range ROH = 1.0-1.6 A, in contrast to the relatively deep single minimum function in the ground state. Furthermore, we obtained very shallow double minima in the excited state potential energy profile of SA and 3ASA in contrast to the single minimum observed in the previous work. The change of potential energy profile along the reaction path induced by the substitution of electron donating groups (-NH2 and -OCH3) at different sites has been investigated. Substitution at para position with respect to the phenolic OH group showed strong suppression of excited state proton dislocation compared with unsubstitued SA, while substitution at ortho position hardly affected the shape of the ESIPT curve. The TDDFT results are discussed in comparison with those of CASPT2 method.

• Nuclear Medicine and Molecular Imaging
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• 제43권1호
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• pp.1-9
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• 2009

As many new drug substances contained various aromatic rings and fluorine attached to an electron rich aromatic ring or on the meta-position, a strategy towards improvement in aromatic fluorination of these compounds is highly desirable. The introduction of fluorine-18 onto aromatic rings showed in the limited condition containing electron withdrawing group (EWG) on the para- or ortho-position to get reasonable radiochemical yield so far. No-carrier added (NCA) [$^{18}F$]fluoroarene syntheses by iodonium salts recently reported that has the potential to greatly increase the yield in systems or positions that normally not reactive enough to give sufficient yields in simple model reaction. This review describes the methodological approach towards effective aromatic fluorination by diaryliodonium salts and future prospects in an application of novel PET radiotracer.

• 천문학회보
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• 제35권1호
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• pp.69.1-69.1
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• 2010

IC 443 is famous for its interaction with nearby molecular clouds and intense H2 emission lines in infrared. Therefore, it has been studied extensively for the understanding of molecular shocks. We observed H2 mission lines toward the shock-cloud interaction regions of IC 443, known as clumps B, C, and G. The observations were performed with the InfraRed Camera (IRC) onboard a satellite AKARI over 2.5-5.0 um, where previous space observations, e.g. Infrared Space Observatory (ISO) and Spitzer, do not cover. Our AKARI observations provide spectra of sequential pure-rotational and ro-vibrational H2 emission lines. For the clumps C and G, combining with previous mid-infrared observational results, we found that the H2 level populations show a significant separation between v=0 and v=1 levels; v=1 levels are under-populated than v=0 levels, therefore, the population cannot be described by two temperature LTE model, as many people have analyzed for the shocked H2 gas. We also applied the thermal admixture model, dN(H2; T)~T^(-b) dT, with varying ortho-to-para ratios according to the temperature, to describe the level population, and obtained plausible ranges of the H2 gas density and power-law index b.

• 분석과학
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• 제17권3호
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• pp.282-288
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• 2004

Inclusion selectivities of the cyanocadmate host complexes with ammonium oniums, $[Cd_x(CN)_{2x}][onium{\cdot}zG]$ (onium = $NMe_3Et^+$, $NMeEt{_3}^+$ and $NEt{_4}^+$, G = guest), have been investigated for $C_6H_6$ (B), PhMe (T), PhEt (E), ortho (O), meta (M), and para (P) isomers of $C_6H_4Me_2$ as the aromatic guest molecules. From the binary, ternary, quaternary and quinary mixed guests of B, T, E, O, M and P, the order of preference in the $NMe_3Et+$-host is $B{\gg}$T>P${\fallingdotseq}O{\fallingdotseq}M$ and E>O${\gg}P{\fallingdotseq}M$; in the $NMeEt{_3}^+$-host is T>B>P${\gg}O{\fallingdotseq}M$ and E>P${\gg}$M>O; in the $NEt{_4}^+$-host is $B{\gg}T{\fallingdotseq}O{\fallingdotseq}M{\fallingdotseq}P$. However, the $NEt{_4}^+$-host complexes of E, O, M and P mixed-guests were not obtained. These inclusion selectivities were compared to our previous results of the $NMe{_4}^+$-host; T>B>P${\gg}$M>O and E>P${\gg}$M>O.

• Mass Spectrometry Letters
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• 제2권1호
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• pp.24-27
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• 2011

Hyperthermal ion/surface collisions of bromotoluene radical cations were studied using perfluorinated (F-SAM) and hydroxyl-terminated (OH-SAM) self-assembled monolayer surfaces in a tandem mass spectrometer with BEEQ geometry. The isomers were differentiated by ion abundance ratios taken from surface-induced dissociation (SID). The dissociation rate followed the order of ortho > meta > para isomers. The peak abundance ratio of m/z 51 to m/z 65 showed the best result to discern the isomers. A dissociation channel leading to tolylium ion was suggested to be responsible for the pronounced isomeric differences. The capability of SID to provide high-energy activation with narrow internal energy distribution may have channeled the reaction into the specific dissociation pathway, also facilitating small differences in reaction rates to be effective in the spectral time window of this experiment. All of the molecular ions experiencing reactive collisions with the F-SAM surface undergo transhalogenation, in which a fluorine atom on the surface replaces the bromine in the incoming ions. This reactive collision was dependent on the laboratory collision energy occurring in ca. 40.75 eV range.

• 천문학회보
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• 제36권2호
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• pp.105.1-105.1
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• 2011

We present the modeling results of deuterium fractionation of water ice, $H_2$, and the primary deuterium isotopologues of $H3^+$ in the physical conditions associated with the star and planet formation process. We calculated the deuterium chemistry for a range of gas temperatures (Tgas~10-30 K) and ortho/para ratio (opr ) of $H_2$ based on state-to-state reaction rates and explore the resulting fractionation including the formation of a water ice mantle coating grain surfaces. We find that the deuterium fractionation exhibits the expected temperature dependence of large enrichments at low gas temperature, but only for opr-H2<0.01. More significantly the inclusion of water ice formation leads to large D/H ratios in water ice (${\geq}10^{-2}$ at 10 K) but also alters the overall deuterium chemistry. For T<20 K the implantation of deuterium into ices lowers the overall abundance of HD which reduces the efficiency of deuterium fractionation at high density. Under these conditions HD will not be the primary deuterium reservoir in the cold dense interstellar medium and $H3^+$ will be the main charge carrier in the dense centers of pre-stellar cores and the protoplanetary disk midplane.

• 대한의생명과학회지
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• 제16권2호
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• pp.123-126
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• 2010

Volatile organic compounds are commonly off gassed from various building materials and can induce sick building syndrome. Volatile organic compounds such as formaldehyde, xylene and toluene are known as toxic agents in immune cells. Human leukocytes, particularly, neutrophils and eosinophils play important roles in the regulation of immune responses. In this study, we investigated the toxic effects of formaldehyde, ortho-xylene (o-xylene), para-xylene (p-xylene) and toluene on the apoptosis of neutrophils and eosinophils isolated from the blood of healthy donors. Formaldehyde increased the constitutive apoptosis of neutrophils and eosinophils. o-xylene, p-xylene and toluene increased the spontaneous apoptosis of eosinophils, but not that of neutrophils. Formaldehyde increased the protein level of IL-8 in neutrophils and eosinophils, and suppressed the MCP-1 expression in neutrophils. The release of IL-6 from neutrophils was diminished by volatile organic compounds used in this study. In conclusion, formaldehyde, xylene and toluene elevate the apoptosis of neutrophils and eosinophils, and regulate the release of cytokine and chemokine in neutrophils and eosinophils. These results indicate that formaldehyde, xylene and toluene have a cytotoxicity in human neutrophils and eosinophils and may damage the modulation of immune responses.

• 대한화학회지
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• 제50권2호
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• pp.107-115
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• 2006

[X=ortho (L1), meta(L2) 및 para(L3)]리간드를 갖는 주석(II) 화합물들을 합성하고, 그 특성을 원소분석, 적외선 분광광도법, 자외선/가시광선 분광광도법 및 열분석법을 이용하여 확인하였다. 자외선 분광광도법을 통하여, 주어진 ONNO 주게 리간드들의 이민(imine) 및 카보닐기의 배위 모드가 C2v 대칭성을 갖는 것으로 나타났다. 또한 열분석 결과, Sn(L3) 화합물이 가장 높은 활성화 에너지를 가지는 반면, Sn(L2) 화합물이 가장 낮은 활성화 에너지를 가짐을 알 수 있었다.

• 한국안전학회지
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• 제16권2호
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• pp.75-79
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• 2001

For handling and storage of reactive chemicals, the hazard evaluations have been extremely important. In the chemical industry, the most concerns are focused on the thermal harzards such as runaway reactions and thermal decompositions, which are mostly governed by thermodynamics and reaction kinetics or these reactive chemical in the system. This study no investigated the thermal decomposition characteristics of nitrophenylhydrazine isomers by using differential scanning calorimeter(DSC) and accelerating rate calorimeter(ARC). Experimental results showed that exothermic onset-temperatures in nitrophenylhydrazine(NPH) isomers were about 160-$210^{\circ}C$ by DSC and 100-$150^{\circ}C$ by ARC. The decomposition temperature acquired by ARC was about 50-$60^{\circ}C$ lower than that by DSC. Reaction heats were about 40-100cal/g by DSC and 330-750ca1/g by ARC. While ortho isomer of NPH show two distinct exothermic peaks, para isomer shows a single peak in DSC curves. The first exothermic peak for 2-NPH is mainly due to intramolecular dehydration forming 1-hydroxybenzotriazole(HOBT) and the second exothermic peak is mainly due to the decomposition of HOBT formed in the first step of decomposition. The exothermin peak in the DSC curve for 4-NPH is mainly due to dissociation of hydrazino and nitro groups.