• BMB Reports
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• 제55권9호
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• pp.439-446
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• 2022

Pyridoxal 5'-phosphate (PLP)-dependent enzymes are ubiquitous, catalyzing various biochemical reactions of approximately 4% of all classified enzymatic activities. They transform amines and amino acids into important metabolites or signaling molecules and are important drug targets in many diseases. In the crystal structures of PLP-dependent enzymes, organic cofactor PLP showed diverse conformations depending on the catalytic step. The conformational change of PLP is essential in the catalytic mechanism. In the study, we review the sophisticated catalytic mechanism of PLP, especially in transaldimination reactions. Most drugs targeting PLP-dependent enzymes make a covalent bond to PLP with the transaldimination reaction. A detailed understanding of organic cofactor PLP will help develop a new drug against PLP-dependent enzymes.

• Computers and Concrete
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• 제7권5호
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• pp.403-419
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• 2010

The bond mechanism for reinforcing bars in concrete is equivalent to the normal contact and friction between the inclined ribs and the surrounding concrete. Based on the contact density model for the computation of shear transfer across cracks, an open-slip coupled model was developed for simulating three-dimensional bond behavior for reinforcing bars in concrete. A parameter study was performed and verified by simulating pull-out experiments of extremely different boundary conditions: short bar embedment with a huge concrete cover, extremely long bar embedment with a huge concrete cover, embedded aluminum bar and short bar embedded length with an insufficient concrete cover. The bar strain effect and splitting of the concrete cover on a local bond can be explained by finite element (FE) analysis. The analysis shows that the strain effect results from a large local slip and the splitting effect of a large opening of the interface. Finally, the sensitivity of rebar geometry was also checked by FE analysis and implies that the open-slip coupled model can be extended to the case of plain bar.

• Journal of The Korean Society of Agricultural Engineers
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• 제54권5호
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• pp.25-34
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• 2012

It has been well known that concrete structures exposed to acid and sulfate environments such as sewer etc. show significant decrease in their durability due to chemical attack. Such deleterious acid and sulfate attacks lead to expansion and cracking in concrete, and thus, eventually result in damage to cement mortar by forming expansive hydration products due to the reaction between cement hydration products and acid and sulfate ions. In this study, the effect of fly ash and blast furnace slag on the bond performances of structural synthetic fiber in latex modified cement mortar under sulfate environments. Fly ash and blast furnace slag contents ranging from 0 % to 20 % are used in the mix proportions. The latex modified cement mortar specimens were immersed in fresh water, 8 % sodium sulfate ($Na_2SO_4$) solutions for 28 and 50 days, respectively. Pullout tests are conducted to measure the bond performance of structural synthetic fiber from latex modified cement mortar after sulfate environments exposure. Test results are found that the incorporation of fly ash and blast furnace slag can effectively enhance the PVA fiber-latex modified cement mortar interfacial bond properties (bond behavior, bond strength and interface toughness) after sulfate environments exposure. The microstructural observation confirms the findings on the interface bond mechanism drawn from the fiber pullout test results under sulfate environments.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1945-1950
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• 2011

The pyridinolysis of methyl phenyl phosphinic chloride is investigated kinetically in acetonitrile at -20.0 $^{\circ}C$. The Hammett and Br${\o}$nsted plots for substituent X variations in the nucleophiles are biphasic concave downwards with a break point at X = H, and unusual positive ${\rho}_X$ (= 2.94) and negative ${\beta}_X$ (= -0.48) values are obtained for the strongly basic nucleophiles. A stepwise mechanism with a rate-limiting step change from bond breaking for the weakly basic pyridines to bond formation for the strongly basic pyridines is proposed on the basis of biphasic concave downward Hammett and Br${\o}$nsted plots. Unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are rationalized by the isokinetic relationship. The pyridinolyses and anilinolyses of four $R_1R_2$P(=O)Cl-type substrates, dimethyl, diethyl, methyl phenyl, and diphenyl phosphinic chlorides in acetonitrile are compared to obtain systematic information on phosphoryl transfer reaction mechanism. The combination of the two ligands, Me and Ph, shows unexpected kinetic results for both the anilinolysis and pyridinolysis: greatest magnitude of $k_H/k_D$ (= 2.10) involving deuterated anilines $[XC_6H_4NH_2(D_2)]$ for the anilinolysis, and exceptionally fast rate and biphasic concave downward free energy correlation for the pyridinolysis.

• Journal of the Korean Society of Combustion
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• 제14권1호
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• pp.9-18
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• 2009

The NOx emission characteristics of DME in counterflow nonpremixed flames were investigated numerically, and brief experiments were carried out to compare the flame shapes and NOx emissions with those of $C_{3}H_{8}$ and $C_{2}H_{6}$. The DME flames were calculated using Kaiser's mechanism, while the $C_{2}H_{6}$ flames were calculated using the $C_3$ mechanism. These mechanisms were combined with the modified Miller-Bowman mechanism for the analysis of NOx. Experimental results show that DME flame has the characteristics of partial premixed flame and the flame length becomes very shorter compared with general hydrocarbon fuels and then, the NOx emission of DME is low as much as 60 % of $C_{3}H_{8}$. In the calculated results of counterflow nonpremixed flames, the $EI_{NO}$ of DME nonpremixed flame is low as much as 50 % of the $C_{2}H_{6}$ nonpremixed flame. The cause of $EI_{NO}$ reduction is attributed mainly to the characteristics of partial premixed flame due to the existence of O atom in DME and partly to the O-C bond in DME, instead of C-C bond in hydrocarbon fuels.

• Steel and Composite Structures
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• 제13권5호
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• pp.473-487
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• 2012

An experimental study was performed to investigate the seismic performance of steel reinforced concrete (SRC) special-shaped columns. For this purpose, 17 steel reinforced concrete special-shaped column specimens under low-cyclic reversed load were tested, load process and failure patterns of the specimens with different steel reinforcement were observed. The test results showed that the failure patterns of these columns include shear-diagonal compression failure, shear-bond failure, shear-flexure failure and flexural failure. The failure mechanisms and characteristics of SRC special-shaped columns were also analyzed. For different SRC special-shaped columns, based on the failure characteristics and mechanism observed from the test, formulas for calculating ultimate shear capacity in shear-diagonal compression failure and shear-bond failure under horizontal axis and oblique load were derived. The calculated results were compared with the test results. Both the theoretical analysis and the experimental results showed that, the shear capacity of T, L shaped columns under oblique load are larger than that under horizontal axis load, whereas the shear capacity of +-shaped columns under oblique load are less than that under horizontal axis load.

• Journal of Welding and Joining
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• 제21권3호
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• pp.58-67
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• 2003

In this study, the formation mechanism of discontinuities in the laser fusion zone of diamond saw blade was investigated. $CO_2$ laser weldings were conducted along the butt between Fe base sintered tip and carbon steel shank with sets of variable welding parameters. The effect of heat input on irregular humps, outer cavity, inner cavity and bond strengh was evaluated. The optimum heat input to have a proper humps was in the range of 10.4~$17.6kJm_{-1}$. With increasing heat input, both outer and inner cavities were reduced. The outer cavity was caused by insufficient refill of keyhole, while inner cavity was caused by trapping of bubble in molten metal. The bubble came from sintered tip and intensive vaporization at bottom tip of the keyhole. A gas formation and low melting point element vaporization were not occurred during welding. We could not find any relationship between bond strength and amount of discontinuities. Because the fracture were occurred in not only sintered tip but also carbon steel shank due to hardness distributions.

• Geomechanics and Engineering
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• 제20권6호
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• pp.517-525
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• 2020

The long-term stability of rock engineering is significantly affected by the time-dependent deformation behavior of rock, which is an important mechanical property of rock for engineering design. Although the hard rocks show small creep deformation, it cannot be ignored under high-stress condition during deep excavation. The inner mechanism of creep is complicated, therefore, it is necessary to investigate the relationship between microscopic creep mechanism and the macro creep behavior of rock. Microscopic numerical modeling of sandstone creep was performed in the investigation. A numerical sandstone sample was generated and Parallel Bond contact and Burger's contact model were assigned to the contacts between particles in DEM simulation. Sensitivity analysis of the microscopic creep parameters was conducted to explore how microscopic parameters affect the macroscopic creep deformation. The results show that the microscopic creep parameters have linear correlations with the corresponding macroscopic creep parameters, whereas the friction coefficient shows power function with peak strength and Young's modulus, respectively. Moreover, the microscopic parameters were calibrated. The creep modeling curve is in good agreement with the verification test result. Finally, the creep curves under one-step loading and multi-step loading were compared. This investigation can act as a helpful reference for modeling rock creep behavior from a microscopic mechanism perspective.

• Proceedings of the KSME Conference
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• 대한기계학회 2008년도 추계학술대회B
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• pp.1973-1978
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• 2008

The NOx emission characteristics of DME in counterflow nonpremixed flames were investigated numerically, and brief experiments were carried out to compare the flame shapes and NOx emissions with those of $C_3H_8$ and $C_2H_6$. The DME flames were calculated using Kaiser's mechanism, while the $C_2H_6$ flames were calculated using the $C_3$ mechanism. These mechanisms were combined with the modified Miller-Bowman mechanism for the analysis of NOx. Experimental results show that DME flame has the characteristics of partial premixed flame and the flame length becomes very shorter compared with general hydrocarbon fuels and then, the NOx emission of DME is low as much as 60% of $C_3H_8$. In the calculated results of counterflow nonpremixed flames, the EINO of DME nonpremixed flame is low as much as 50% of the $C_2H_6$ nonpremixed flame. The cause of $EI_{NO}$ reduction is attributed mainly to the characteristics of partial premixed flame due to the existence of O atom in DME and partly to the O-C bond in DME, instead of C-C bond in hydrocarbon fuels.

• Journal of the Korean Chemical Society
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• 제36권3호
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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.