• Bulletin of the Korean Chemical Society
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• v.22 no.2
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• pp.154-158
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• 2001

The steps for the generation of very thin GaN films on ultrathin AlN/6H-SiC surface by alternating a pulsative supply (APS) of trimethyl gallium and NH3 gases have been examined by ASED-MO calculations. We postulate that the gallium cul ster was formed with the evaporation of CH4 gases via the decomposition of trimethyl gallium (TMG), dimethyl gallium (DMG), and monomethyl galluim (MMG). During the injection of NH3 gas into the reactor, the atomic hydrogens were produced from the thermal decomposition of NH3 molecule. These hydrogen gases activated the Ga-C bond cleavage. An energetically stable GaN nucleation site was formed via nitrogen incorporation into the layer of gallium cluster. The nitrogen atoms produced from the thermal degradation of NH3 were expected to incorporate into the edge of the gallium cluster since the galliums bind weakly to each other (0.19 eV). The structure was stabilized by 2.08 eV, as an adsorbed N atom incorporated into a tetrahedral site of the Ga cluster. This suggests that the adhesion of the initial layer can be reinforced by the incorporation of nitrogen atom through the formation of large grain boundary GaN crystals at the early stage of GaN film growth.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.103-106
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• 2002

A new reaction mechanism is proposed for the reaction of thianthrene cation radical perchlorate $(Th^{+{\cdot}}CIO_4^-}$ and tert-butyl peroxide in acetonitrile at room temperature on the basis of experimental and theoretical results. Rapid C-O bond rupture instead of O-O bond cleavage was observed by a good peroxy radical trapping agent, thianthrene cation radical. Products were N-tert-butyl acetamide, thianthrene 5-oxide (ThO), thianthrene 5,5-dioxide $(SSO_2)$, and thianthrene (Th). Thianthrene 5,10-dioxide (SOSO) was not obtained. A comparative computational study of the cation radical of tert-butyl peroxide is made by using B3LYP and CBS-4. The computational results are helpful to explain the reaction mechanism.

• Mass Spectrometry Letters
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• v.10 no.2
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• pp.50-55
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• 2019

The fragmentation statistics of ion trap CID (Collision-Induced Dissociation) spectra using 87,661 tandem mass spectra of doubly charged tryptic peptides are analyzed here. In contrast to the usual method of using intensity information, the frequency of occurrence of fragment ions, with respect to the position of the cleavage site and the residues at these sites is studied in this paper. The analysis shows that the frequency of occurrence of fragment ion peaks is more towards the middle of the peptide than its ends. It was noted that amino acid with an aromatic and basic side chain at N- & C- terminal end of the peptide stimulates more peaks at the lower end of the spectrum. The residue pair effect was shown when the amide bond occurs between acidic and basic residues. The fragmentation at these sites (D/E-H/R/K) stimulates the generation of the y-ion peak. Also, the cleavage site H-H/R/K stimulates the generation of b-ions. K-P environment in the peptide sequence has more tendency to generate y-ions than b-ions. Statistical analysis helps in the visualization of the CID fragmentation pattern. Cleavage pattern along the length of the peptide and the residue pair effects, enhance the knowledge of fragmentation behavior, which is useful for the better interpretation of tandem mass spectra.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2301-2305
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• 2011

The potential energy surface (PES) for the loss of HCN or HNC from the pyrazine molecular ion was determined based on quantum chemical calculations using the G3//B3LYP method. Four possible dissociation pathways to form four $C_3H_3N^{+{{\bullet}}$ isomers were examined. A Rice-Ramsperger-Kassel-Marcus quasi-equilibrium theory model calculation was performed to predict the dissociation rate constant and the product branching ratio on the basis of the obtained PES. The resultant rate constant for the HCN loss agreed with the previous experimental result. The kinetic analysis predicted that the formation of $CH=CHN{\equiv}CH^{+{\bullet}}+HCN$ was predominant, which occurred by three consecutive steps, a C-C bond cleavage to form a linear intermediate, a rearrangement to form an H-bridged intermediate, and elimination of HCN.

• YAKHAK HOEJI
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• v.34 no.5
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• pp.296-301
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• 1990

Irradiation of the berberinephenolbetaine in a stream of argon produced the 8,14-cycloberberines [1]. On treatment with ethylchloroformate $C_8-N$ bond cleavage of the compound [1] occurred, accompanied with dehydrochlorination to give 7-ethylcarboxyisoquinoline [3], and the product [3] treated with strong alkali solution to give the 13-oxonorotensane [4] in 64% yield. Irradiation of the compound [4] converted easily to dihydro-8H-dibenzo[a, g] quinolizine-8-one [5]. and then the compound [5] was treated with methyliodide to give the 8-oxo-quinolizinium methiode. The intermediate colume chromatography on IRA-400 afforded the benzo[c, g]azecine-5-one[6] in 63% yield. The results of biological activities for these compounds are also presented.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.19 no.1
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• pp.45-51
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• 1986

Equimolar aqueous solutions of D-glucose and glycine were heated at $50^{\circ}C\;and\;95^{\circ}C$ at pH 6.7. The headspace volatiles and the ether extracts from the reaction mixture were analyzed by gas chromatography and gas chromatography-mass spectrometry using a fused silica capillary column. The major components formed were identified as diacetyl, three furfurals, two pyrroles, one furanone, two pyranones and two amides. In order to elucidate the formation mechanisms of the amides formed front amino-carbonyl reaction, two model systems were adopted. N-butylacetamide were formed as major components from diacetyl-butylamine ana glyoxal-butylamine systems, respectively. The results obtained suggest that such ${\alpha}-dicarbonyls$ as 3-deoxy-D-erythro-2,3-hexodiulose and diacetyl generated in the amino-carbonyl reaction react with amino compounds, amides then being formed by cleavage of the C-C bond in the ${\alpha}-dicarbonyls$.

• Proceedings of the Korean Vacuum Society Conference
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• 1999.07a
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• pp.181-181
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• 1999

Self-assembled monolayers(SAMs) of alkanethiol have been formed on the Cu(111) surfaces in vacuum. The thermal behavior of octanethiol-based SAMs on the Cu(111) surface have been examined in ultrahigh vacuum. Using X-ray photoelectron spectroscopy (XPS), it is found that the monolayers are stable up to about 500K in vacuum. Decomposition is signaled by a decrease in the intensity of C ls peak, accompanied by an increase of the intensity of the Cu 2p peak. However, the intensity of the S 2p peak doesn't change much as a function of annealing temperature. Thermal the decomposition mass spectra show that n-alkene is the predominant species desorbing from the surface in the 500-600K temperature range. The totality of these data leads to the conclusion that the monolayers decompose through the S-C bond cleavage by hydrogen elimination reaction, resulting in the desorption of hydrocarbon moiety as n-alkene. Following this initial decomposition step, Cu2S layers are observed on the surface. For comparison, attempts were also made to examine the thermal behavior of octanethiol-based SAMs on the Cu(111) surface in air. It has been shown that the SAMs on the Cu(111) surfaces begin to desorb with the oxidation of the thiolate to sulfonate at 400K. Upon annealing to 450K, the monolayer has almost completely desorbed as indicated by the virtual disappearance of the S 2p peak.

• YAKHAK HOEJI
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• v.40 no.6
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• pp.621-624
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• 1996

Betaine was treated with hydrochloric acid and then with sodium borohydride to give a hydroxy compound 2. The reaction of 2 with thionyl chloride followed by thiourea led a comp ound 5. Oxidation of compound 2 with pyridinium dichromate(PDC) and succesive treatment with Lawesson's reagent also afforded the same compound 5. Cleavage of N-C14 bond compound of 7 was carried out via two reaction sequence from the compound 4. Finally, compound 10 was sythesized by a series of transformations from the compound 4.

• Analytical Science and Technology
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• v.24 no.2
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• pp.78-84
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• 2011

The fragmentation patterns of a serine protease inhibitor, camostat, and its degradation product, 4-(4-guanidinobenzoyloxy)phenylacetic acid (GBPA), were for the first time investigated by a triple quadrupole tandem mass spectrometry equipped with an electrospray source (ESI-MS/MS) in positive and/or negative ion mode under collision-induced dissociation (CID). The positive CID spectrum of camostat showed distinctly that the single bond (C-O) cleavage between carbonyl group and oxygen atom of the ester bonds of the compound favorably occurred and then the loss of N,N-dimethylcarbamoylmethyl group was more susceptible than that of guanidine moiety. In the positive ion CID spectrum of GBPA, the initial cleavage between the carbonyl group and oxygen atom of 4-guanidinobenzoyloxy group also occurred, yielding the most abundant fragment ion at m/z 145. On the other hand, the negative CID spectrum of GBPA characteristically showed the occurrence of the most abundant peak at m/z 226 resulting from the sequential neutral losses of $CO_2$ and HN=C=NH from the parent ion at m/z 312.

• Journal of Photoscience
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• v.1 no.1
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• pp.31-37
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• 1994

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.