• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.366-375
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• 1992

The aminolysis of carbamates are studied MO theoretically using AM1 method. The results indicated that the reactivity is determined by bond-making and-breaking and steric effects; as a result the $B_{AC}2$ mechanism is favored due to favorable contribution of bond formation in agreement with experimental results. We found that although thermal 2＋2 reaction is forbidden, it becomes allowed when the total electrons involved are six in a four-center reaction and proceeds by a consecutive onestep mechanism. Comparison of activation barriers show that greater energy is required in breaking a sigma bond compared with the energy required for breaking a $\pi$ bond, by 17 kcal/mol and the six membered ring structure is favored about 5 kcal/mol sterically.

• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.917-920
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• 2007

Ketene-forming eliminations from C4H3(S)CH2C(O)O-C6H3-2-X-4-NO2 (1) promoted by R2NH in MeCN have been studied kinetically. The reactions are second-order and exhibit Bronsted β =0.51-0.62 and |βlg|= 0.47-0.53. Hence, an E2 mechanism is evident. The Bronsted β increased from 0.33 to 0.53 and |βlg| remained nearly the same by the change of the base-solvent from Bz(i-Pr)NH/Bz(i-Pr)NH2+ in 70 mol% MeCN(aq) to Bz(i-Pr)NH-MeCN, indicating a change to a more symmetrical transition state with similar extents of Cβ -H and Cα -OAr bond cleavage. When the β-aryl group was changed from thienyl to phenyl in MeCN, the β value increased from 0.53 to 0.73 and |βlg| decreased from 0.53 to 0.43. This indicates that the transition state became skewed toward more Cβ -H bond breaking with less Cα-OAr bond cleavage. Noteworthy is the greater double bond stabilizing ability of the thienyl group in the ketene-forming transition state.

• Journal of Microbiology and Biotechnology
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• v.33 no.12
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• pp.1606-1614
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• 2023

Biochemical gut metabolism of dietary bioactive compounds is of great significance in elucidating health-related issues at the molecular level. In this study, a human gut bacterium cleaving C-C glycosidic bond was screened from puerarin conversion to daidzein, and a new, gram-positive C-glycoside-deglycosylating strain, Dorea sp. MRG-IFC3, was isolated from human fecal sample under anaerobic conditions. Though MRG-IFC3 biotransformed isoflavone C-glycoside, it could not metabolize other C-glycosides, such as vitexin, bergenin, and aloin. As evident from the production of the corresponding aglycons from various 7-O-glucosides, MRG-IFC3 strain also showed 7-O-glycoside cleavage activity; however, flavone 3-O-glucoside icariside II was not metabolized. In addition, for mechanism study, C-glycosyl bond cleavage of puerarin by MRG-IFC3 strain was performed in D₂O GAM medium. The complete deuterium enrichment on C-8 position of daidzein was confirmed by ¹H NMR spectroscopy, and the result clearly proved for the first time that daidzein is produced from puerarin. Two possible reaction intermediates, the quinoids and 8-dehydrodaidzein anion, were proposed for the production of daidzein-8d. These results will provide the basis for the mechanism study of stable C-glycosidic bond cleavage at the molecular level.

• Journal of the Korea institute for structural maintenance and inspection
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• v.23 no.3
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• pp.150-159
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• 2019

The bond analysis model equation was proposed through the regression analysis of the experimental values of bond behavior for each rebar. In order to verify the appropriateness of the bond analysis model equation, the bond behaviors calculated by the proposed bond analysis model, BPE model and CMR model were compared with experimental values. The proposed bond model showed the closest behavior to the experimental values when compared to other analysis models. The former models can not consider the different properties of GFRP rebar according to composed materials, mixing and manufacturing method and the latter has limitation to express the relationships between bond behavior because of derived formula by numerical analysis. This study proposed the analytical model different considering bond mechanism according to surface type. In order to verity the appropriateness of the bond analytical model, the bond behaviors calculated by the proposed bond analytical model, BPE model and CMR model were compared with experimental values. The proposed bond model showed the closest behavior to the experimental values when compared to other analysis models.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.141-155
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• 2014

Peptide bond hydrolysis는 세포 내외의 생화학반응에 있어서 핵심이다. 하지만 amide Hydrolysis Mechanism은 아직 명확하게 규명되지 않았다. pH가 중성인 물에서의 비 촉매 가수분해가 발생하는 몇몇 실험적 증거가 있지만, 해당 반응 매커니즘은 4 가지(non-assisted concerted, non-assisted step-wise, assisted concerted, assisted step-wise)로 여전히 논란이 있다. 이번 연구에서는, Formamide의 가능한 Hydrolysis Mechanism을 자세히 연구해보고자 한다. 먼저, Ab-initio 계산을 통해 4가지 반응 메커니즘의 다시 한번 확인하고, quantum chemical calculations과 quantum mechanical molecular dynamic이 결합된 (QMMD) simulation을 통하여 water solvent에서의 반응 메커니즘의 에너지관계를 규명하였다. 결론적으로 아직 계산이 끝나지 않은 supported concerted mechanism을 제외한 모든 계산에서 non-supported, supported 두 system 모두에서 step-wise가 일어나기 쉬웠고, non-supported 보다 supported mechanism이 선호됨을 보였다. Intermediate인 amino-gem-diol의 수용액 상에서 안정화 또한 나타났다. 이는 Ab-initio 계산만 통해서는 정확하게 산출할 수 없는 엔트로피의 영향을 잘 보여준다.

• Proceedings of the Korea Concrete Institute Conference
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• 2004.05a
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• pp.84-87
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• 2004

Nominal flexural strength of RC members strengthened with FRP sheets is generally based on the tensile strength of composite materials obtained from coupon tests. This method is based on the assumption that bond failure does not occur until the FRP sheet reaches its rupture strength. According to the previous researches, however, bond failure often occurs before the FRP sheet reaches its rupture strength. Some attempts were made to control debonding failure by increasing the bonded length of sheet or wrapping the section around their side of the member(U-wrap). In this study, the flexural failure mechanism of RC beams strengthened with AFRP sheets with different bond lengths is investigated. Their strengthening details to prevent the premature debonding failure are also suggested and its effectiveness is verified.

• International Journal of Fuzzy Logic and Intelligent Systems
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• v.5 no.2
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• pp.108-113
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• 2005

This paper suggests a control method for an efficient topology/parameter evolution in a bond graph-based GP design framework that automatically synthesizes designs for multi-domain, lumped parameter dynamic systems. We adopt a hierarchical breeding control mechanism with fitness-level-dependent differences to obtain better balancing of topology/parameter search - biased toward topological changes at low fitness levels, and toward parameter changes at high fitness levels. As a testbed for this approach in bond graph synthesis, an eigenvalue assignment problem, which is to find bond graph models exhibiting minimal distance errors from target sets of eigenvalues, was tested and showed improved performance for various sets of eigenvalues.

• The Korean Journal of Food And Nutrition
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• v.5 no.1
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• pp.23-32
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• 1992

Kinetic studies of nucleophilic substitution reactions of dansyl, bansyl, dabsyl chlorides with pyridines have been investigated at $0^{\circ}C$ in a range of methanol-acetonitrile binary solvent mixtures. The order of magnitude for reactivity of substrates with pyridines in the same reaction condition is dabsyl chloride>dansyl chloride> bansyl chloride. The value of $\rho$n(-2.29~ -4.66) and $\beta$(0.537~0.901) associated with a change substituent in the nucleophile are large and indicate a relatively advanced bond formation in the transition state. Solvatochromic correlations were predicted the increase of bond formation transition state according to the increasing MeCN contents, showing the greater contribution of polarity polarizability ($\pi$*) than hydro-gen bond donar acidity($\alpha$). We conclude that the reactions of dansyl, bansyl, dabsyl chlorides with pyridines proceed via associative Sn2 type reaction mechanism.

• YAKHAK HOEJI
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• v.28 no.2
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• pp.101-127
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• 1984

The study of interaction between riboflavin derivatives and biologically active substances was reviewed. With combination of spectroscopic methods such as NMR, UV, Fluorescence and IR, informations about interaction mechanism including hydrogen bond formation, conformation of association complex, and association constant were obtained. 1. Riboflavin associated with adenine but not with other bases found in the nucleic acids. -CONHCO- group was included in the formation of hydrogen bond with adenine. 2. Riboflavin interacted with alcohol to make a 1 : 1 association complex through the 3N-imino and 2C-carbonyl group of the isoalloxazine ring and the hydroxyl group of the alcohols. 3. Riboflavin associated with salicylates to produce the cyclic hydrogen-bonded dimer. The strongest complex was formed with salicylic acid, a weaker one with aspirin, and an even weaker one with salicylamide. 4. Other bio-active substances, orotic acid and inhibitors such as phenol, trichloroacetic acid and indol also formed hydrogen bond with riboflavin. 5. Reduced riboflavin showed strong self-association to produce the cyclic hydrogen-bonded complex and it associated with adenine and with cytosine to form 1 : 3 complex.

• Journal of the Korean Society of Manufacturing Technology Engineers
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• v.9 no.6
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• pp.96-102
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• 2000

Spinning mechanism is generally used in coasting process on grass plates. Rebounding PR(Photo Resist) which leads to occur inferiority of coating process is caused by vibrational energy of whole coating system. In this study, the sensitivity analysis is performed to analyze and reduce vibrational terms in the spin coating system. The sensitivity analysis is bared on the numerical expression of this system. By the bond graph method. power flow of each system is represented by some basic bond graph elements. Any energy domain system is modeled using the unified elements. The modelled spin coater system is verified with power spectrum data measured by FFT analyzer. As the results of verifying model parameters and sensitivity analysis, principal factors causing vibration phenomenon are mentioned. A study on vibration method in the spin coating system is discussed.