• Weed & Turfgrass Science
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• v.6 no.1
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• pp.28-31
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• 2017

The mutation rate of proline in the position 197 (Pro197) in acetohydroxy acid synthase (AHAS) is highest among sulfonylurea (SU) herbicide-resistance mutants. Therefore, it is significant to investigate the resistance mechanism for the mutation and to develop the herbicides specific to the mutants. SU herbicide resistance mechanism of the mutants, 197Ser, 197Thr and 197Ala, in AHAS were targeted for designing new SU-herbicide. We did molecular dynamics (MD) simulation for understanding SU herbicide-resistance mechanisms of AHAS mutants and designed new herbicides with docking and MD evaluations. We have found that mutation to 197Ala and 197Ser enlarged the entrance of the active site, while 197Thr contracted. Map of the root mean square derivation (RMSD) and radius gyrations (Rg) revealed the domain indicating the conformations for herbicide resistant. Based on the enlarging-contracting mechanism of active site entrance, we designed new herbicides with substitution at the heterocyclic moiety of a SU herbicide for the complementary binding to the changed active site entrances of mutants, and designed new herbicides. We confirmed that our screened new herbicides bonded to both AHAS wild type and mutants with higher affinity, showing more stable binding conformation than the existing herbicides.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Structural Engineering and Mechanics
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• v.85 no.2
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• pp.275-287
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• 2023

The use of environmental-friendly building materials is becoming increasingly popular worldwide. Compared to the normal concrete, rubber-based concrete is considered more durable, environmentally friendly, socially and economically viable. In this investigation, M20 grade concrete was designed and the fine aggregates were replaced with crumb rubber of two different micron sizes (0.221 mm and 0.350 mm). Fly ash (FA) and silica fume (SF) replaces the binder as supplementary cementitious materials at a rate of 0, 5, 10, 15, and 20% by weight. The mechanical properties of concrete including compressive strength, tensile, and flexural strength were determined. The polynomial work expectation validates the response surface approach (RSM) concept for optimizing SF and FA substitution. The maximum compressive strength (22.53 MPa) can be observed for the concrete containing 10% crumb rubber, 15% fly ash and 15% silica fume. The reduced unit weight of the rubberized concrete may be attributed to the lower specific gravity of the rubber particles. Two-way ANOVA with a significance criterion of less than 0.001 has been utilized with modest residual error from the lack of fit and the pure error. The predictive model accurately forecasts the variable-response relationship. Since, the crumb rubber is obtained from wasted tires incorporating FA and SF as a cementitious ingredient, it helps to significantly improve mechanical properties of concrete and reduce environmental degradation.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1218-1242
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• 2002

Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2017.05a
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• pp.80-80
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• 2017

Titanium and its alloys that have a good biocompatibility, corrosion resistance, and mechanical properties such as hardness and wear resistance are widely used in dental and orthopedic implant applications. However, they do not form a chemical bond with bone tissue. Plasma electrolytic oxidation (PEO) that combines the high voltage spark and electro-chemical oxidation is a novel method to form ceramic coatings on light metals such as tita-nium and its alloys. This is an excellent re-producibility and economical, because the size and shape control of the nano-structure is relatively easy. Silicon (Si), manganese (Mn), and magne-sium (Mg) have a useful to bone. Particularly, Si has been found to be essential for normal bone, cartilage growth, and development. Mn influences regulation of bone remodeling be-cause its low content in body is connected with the rise of the concentration of calcium, phosphates and phosphatase out of cells. Pre-studies have shown that Mg plays very im-portant roles in essential for normal growth and metabolism of skeletal tissue in verte-brates and can be detected as minor constitu-ents in teeth and bone. In this study, Electrochemical behavior of plasma electrolytic oxidized films formed in solution containing Mn, Mg and Si ions were researched using various experimental in-struments. A series of Si-Mn-Mg coatings are produced on Ti dental implant using PEO, with the substitution degree, respectively, at 5 and 10%. The potentiodynamic polarization and AC impedance tests for corrosion behav-iors were carried out in 0.9% NaCl solution at similar body temperature using a potentiostat with a scan rate of 1.67mV/s and potential range from -1500mV to + 2000mV. Also, AC impedance was performed at frequencies anging from 10MHz to 100kHz for corrosion resistance.

• Journal of Korea Foundry Society
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• v.26 no.1
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• pp.17-26
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• 2006

The substitution of cooling method from water quenching to air cooling after solution heat treatment was aimed for the development of a convenient and economical heat treatment process of duplex stainless steels without deterioration of mechanical and corrosion resistant properties for the industry. In order to achieve this goal, the mechanical properties and corrosion properties of a ASTM A890-4A duplex stainless steel were systematically investigated as functions of casting condition and cooling method after solution heat treatment. A 3-stepped sand mold and a permanent Y-block mold were used to check the effects of solidification structure and cooling rate after solution heat treatment. The microstructural characteristics such as the ferrite/austenite phase ratio and the precipitation behavior of ${\sigma}$ phase and carbides were investigated by combined analysis of OM and SEM-EDX with an aid of TTT diagram. Hardness and tension test were performed to evaluate the mechanical properties. Impact property at $-40^{\circ}C$ and corrosion resistance were also examined to check the possibility of the industrial application of this basic study. Throughout this investigation, air-cooling method was proved to effectively substitute for water-quenching process after the solution heat treatment, when the duplex stainless steel was sand mold cast with a thickness below 15 mm or permanent mold cast with a thickness below 20 mm.

• Journal of the Society of Disaster Information
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• v.13 no.3
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• pp.348-357
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• 2017

In this study, we examined the physical properties of cement mortar by replacing a part of the amount of fine aggregate in moist mud flat. I analyzed the possibilities of using bricks. Flow measurement results show that the flow value increases as the mixing ratio of cement and fine aggregate increases and the flow value decreased as the replacement ratio of moist mud flats decreased. Chloride contents were also found to decrease with decreasing substitution rate of moist mud flats. As a result of the compressive strength measurement, the compressive strength increased in inverse proportion as the displacement ratio of moist mud flats decreased in most mixing ratio. As a result of tensile strength measurement, the tendency was similar to compressive strength and the intensity increased as the replacement ratio of moist mud flats decreased.

• Journal of the Korea Institute of Building Construction
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• v.24 no.2
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• pp.215-226
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• 2024

This study presents an experimental investigation into the performance of self-sensing grout formulated with a high volume of ultra-fine fly ash(UHFA). To explore the potential benefits of alternative cementitious materials, the research examined the effect of substituting UHFA with equal parts of blast furnace slag(BFS) fine powder. Both UHFA and BFS are byproducts generated in significant quantities by industrial processes. The evaluation focused on the fresh properties of the grout, including its flow characteristics, as well as the hardened properties such as compressive strength, dimensional stability(length change rate), and electrical properties. The experimental results demonstrated that incorporating UHFA resulted in a substantial reduction in the plastic viscosity of the grout, translating to improved flowability. Additionally, the compressive strength of the UHFA-modified grout surpassed that of the reference grout(without UHFA substitution) at all curing ages investigated. Interestingly, the electrical characteristics, as indicated by the relationships between FCR-stress and FCR-strain, exhibited similar trends for both grout mixtures.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• Journal of Surface Science and Engineering
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• v.26 no.2
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• pp.87-107
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• 1993

The grain size of the final products of WC-Co and WC-Ni composite powders is dependent on the size of the starting material and the conditions employed for the reduction and carburization. APT-Co and -Ni com-plex salts were prepared by the substitution reaction between ammonium ions in APT and the metal ions in Co(NO3)2 and Ni(NO3)2 solutions of different concentrations(0.1 to 0.7M) at $50^{\circ}C$ and the grain sizes of the com-plex salts was $0.54~0.76\mu\textrm{m}$. The complex which calcined the complex salts at $700^{\circ}$~80$0^{\circ}C$ for 60min. were 0.2~0.5$\mu\textrm{m}$. W-Co($5.92^{\circ}C$) and -Ni(6.95%) powders which reduced the complex oxides with H2d atmo-sphere(flow rate;600cc/min.) at $700^{\circ}$~$800^{\circ}C$ for 60min. were $0.5~0.6\mu\textrm{m}$. The mean grain sizes of WC-Co and WC-Ni composite powders which carburized both complex metals of W-Co and W-Ni at $800^{\circ}C$ for 60min. were $0.5~0.6\mu\textrm{m}$, and take place the coarsening of the grain above $800^{\circ}C$ and the optmium ratio of C3H8 and H2 was 0.2 for the control of the free carbon. The effect of Co contents on the particle sizes decreased from 0.4 to $0.25\mu\textrm{m}$ with increasing the content from 2.0 to 7.6w%. The activation energies on the reductions of oxides and the formations of carbides were as follows ; W-Co : Q = 8.7 kcal/mole, W-Ni : Q = 8.1 kcal/mole, WC-Co pow-der : Q = 17.8 kcal/mole, WC-Ni powder : Q = 16.6 kcal/mole.