• Journal of the Korean Magnetic Resonance Society
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• v.3 no.1
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• pp.44-51
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• 1999

An enzyme derived conformational changes of cobalamine is thought to be important in the homolytic cleavage of Co-C bond which is the first step of catalytic Cl-cycle of coenzyme B12-dependent enzymes. Modern 2D-NMR and NMR-based distance geometric studies were carried out to determine the 3D structure of corrin ring. Homonuclear and heteronuclear correlation NMR experiments were performed for complete 1H-NMR signal assignments. Distances between numerous proton pairs were deduced based on the NOE cross peak intensities and subsequently used as input into the distance geometry program for the 3D structure determination. The detailed 3D structure from the present NMR-based analysis was compared with the result from X-ray crystallographic study, which revealed greater conformational changes occur in benzimidazole group and sugar ring than in macrocyclic corrin and tetrapyrrole. In addition, the distance geometry used in this study was found to be quite useful for NMR-based structure determination of medium-sized molecules that give poor NOE effects arising from their intermediate tumbling rate ($\omega$$\tau$c 1.0).

• 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.

• Journal of the Korean Chemical Society
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• v.13 no.3
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• pp.215-219
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• 1969

The kinetics of the reaction of m-or p-substituted benzyl bromides with thiourea in methanol at 35.0$^{\circ}$were determined by an electric conductivity method. According to a plot of log k against the Hammett substituent constants, C-Br bond cleavage in benzyl bromide is postulated to be a rate determining step at the SN2 reaction of benzyl bromide with thiourea. Both electron-donating substituents and electron-withdrawing substituents quantitatively affected the rate of reaction, but each in a different manner. A mechanistic possibility was proposed to account for the results. Some activation parameters were also calculated.

• BMB Reports
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• v.37 no.3
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• pp.304-313
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• 2004

Three-dimensional (3D) models for the 65-kDa activated Cry4A and Cry4B $\delta$-endotoxins from Bacillus thuringiensis subsp. israelensis that are specifically toxic to mosquito-larvae were constructed by homology modeling, based on atomic coordinates of the Cry1Aa and Cry3Aa crystal structures. They were structurally similar to the known structures, both derived 3D models displayed a three-domain organization: the N-terminal domain (I) is a seven-helix bundle, while the middle and C-terminal domains are primarily comprise of anti-parallel $\beta$-sheets. Circular dichroism spectroscopy confirmed the secondary structural contents of the two homology-based Cry4 structures. A structural analysis of both Cry4 models revealed the following: (a) Residues Arg-235 and Arg-203 are located in the interhelical 5/6 loop within the domain I of Cry4A and Cry4B, respectively. Both are solvent exposed. This suggests that they are susceptible to tryptic cleavage. (b) The unique disulphide bond, together with a proline-rich region within the long loop connecting ${\alpha}4$ and ${\alpha}5$ of Cry4A, were identified. This implies their functional significance for membrane insertion. (c) Significant structural differences between both models were found within domain II that may reflect their different activity spectra. Structural insights from this molecular modeling study would therefore increase our understanding of the mechanic aspects of these two closely related mosquito-larvicidal proteins.

• Bulletin of the Korean Chemical Society
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• v.32 no.4
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• pp.1253-1257
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• 2011

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at $50^{\circ}C$ formed well-ordered SAMs with a $(2{\surd}3{\times}{\surd}5)R41^{\circ}$ packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments ($C_5H_9^+$, m/e = 69) generated via C-S bond cleavage and the parent molecular species ($C_5H_9SH^+$, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.

• 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 ${\alpha}-dicarbonyls$.

• 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 the Korean Chemical Society
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• v.15 no.5
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• pp.256-265
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• 1971

An ESR study has been made on free radicals produced in frozen aqueous solutions (ices) of glycine, DL-${\alpha}$-alanine, DL-serine, L-cysteine, DL-leucine and DL-isoleucine by gamma-irradiation at dry ice temperature. All free radicals induced were decayed concomitant to the successive annealing but the radical species which is believed to be dominant seems to be stable even near the melting point of the ice. These dominant species were found to be identical to those resulted from direct action of radiation in the solid at room temperature. Small but significant changes in the spectra of glycine and DL-${\alpha}$-alanine were observed by varying the microwave power. These results seem to support the view that the spectra obtained were composite consisting of more than two different resonances having different power saturation characteristics. The relative contribution of unidentified resonances to the composite spectra was greater for solutions of low concentration. These resonances are assumed to be induced by indirect effects, mainly hydrogen abstraction by radiation produced hydroxyl radicals and also C-N bond cleavage by hydrated electrons.

• Journal of Soil and Groundwater Environment
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• v.26 no.4
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• pp.1-7
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• 2021

The removal of PCBs (Polychlorinated biphenyls) in aqueous phase was investigated in the ultraviolet (UV) process, ultrasonics (US) process and ultraviolet/ultrasonic (UV/US) process using PCB No.7 and Aroclor 1260. For PCB No.7 relatively high removal efficiency over 90% was obtained during 20 min in the UV process and UV/US process. On the other hand, lower removal efficiency of 50 - 70% was achieved for it consisted of individual congeners of PCBs containing 3~8 of chlorine atom. It was found that the dechlorination reaction (the photolytic cleavage of C-Cl bond) was considered as a main removal mechanism in the UV process while PCBs were removed by cavitation-induced radical reaction in the US process. No significant dechlorination occurred in the US process. Consequently, it was suggested that the UV process or UV/US process was applicable for the removal of PCBs in aqueous phase in terms of the removal efficiency and operation time. In addition, the application of saturating gas such as Ar and Air could be considered to control redox condition and enhance the severity of acoustic cavitation for the removal of PCBs.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2213-2218
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• 2012

Efficient synthetic routes were developed to prepare a sizable amount (4-15 grams) of the chiral epoxides 4-6 as versatile intermediates for the synthesis of aspartyl protease inhibitors of therapeutic interest such as HIV protease and ${\beta}$-secretase. Oxidative cleavage of the C(2)-C(3) double bond of L-ascorbic acid followed by functional group manipulation led to the preparation of the epoxide 10, which was opened with an azide to yield a common aziridine intermediate 12. Through opening of the aziridine ring of 12 with either a carbon or a sulfur nucleophile, chiral epoxide precursors 4-6 could be prepared for various HIV protease inhibitors. Except for the final low melting epoxides 5 and 6, all intermediates were obtained as crystalline solids, thus the synthetic pathway can be easily applied to a large-scale synthesis of the chiral epoxides.