• Bulletin of the Korean Chemical Society
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• 제33권2호
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• pp.663-669
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• 2012

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3355-3360
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• 2011

The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $-15.0^{\circ}C$. The studied substrate of 1,2-phenylene phosphorochloridate is cyclic five-membered ring of phosphorus ester, and the anilinolysis rate of 1 is much faster than its acyclic analogue (4: ethyl phenyl chlorophosphate) because of extremely small magnitude of the entropy of activation of 1 compared to 4. The Hammett and Bronsted plots exhibit biphasic concave upwards for substituent X variations in the nucleophiles with a break point at X = 3-Me. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) change from secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines to primary normal ($k_H/k_D$ > 1) with the weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the transition state (TS) variation from a predominant backside attack to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. The primary normal DKIEs are substantiated by a hydrogen bonded, four-center-type TS.

• Bulletin of the Korean Chemical Society
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• 제33권6호
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• pp.1879-1884
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• 2012

The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2003-2008
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• 제12권3호
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• pp.265-270
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• 1991

Theoretical calculations on the stabilization energies of framework atoms in hydrolyses Co(Ⅱ )-exchanged zeolite A were made using some potential energy functions and optimization program. The protons which are produced by hydrolysis of $[Co(H_2O)_n]^{2+}$ ion in large cavity showed a tendency to attack the framework oxygen atom O(1) preferentially, and the oxygen atom O(4) within OH- ion was coordinated at Al atom. The weakness of bonds between T(Si, Al) and oxygen by attack of proton and too large coordination number around small aluminum atom will make the framework of Co(Ⅱ)-exchanged zeolite A more unstable. The stabilization energy of $Co_4Na_4$-A framework (- 361.57 kcal/mol) was less than that of thermally stable zeolite A($Na_{12-}$A: - 419.68 kcal/mol) and greater than that of extremely unstable Ba(Ⅱ)-exchanged zeolite A($Ba_{6-}$A: - 324.01 kcal/mol). All the data of powder X-ray diffraction, infrared and Raman spectroscopy of Co(Ⅱ)-exchanged zeolite A showed the evidence of instability of its framework in agreement with the theoretical calculation. Three different groups of water molecules are found in hydrated Co(Ⅱ )-exchanged zeolite A; W(Ⅰ) group of water molecules having only hydrogen-bonds, W(Ⅱ) group water coordinated to $Na^+$ ion, ans W(Ⅲ) group water coordinated to Co(Ⅱ) ion. The averaged interaction energy of each water group shows the decreasing order of W(Ⅲ)>W(Ⅱ)>W(Ⅰ).

• 한국분말재료학회지
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• 제28권4호
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• pp.342-351
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• 2021

Because of its unique properties, tungsten is a strategic and rare metal used in various industrial applications. However, the world's annual production of tungsten is only 84000 t. Ammonium paratungstate (APT), which is used as the main intermediate in industrial tungsten production, is usually obtained from tungsten concentrates of wolframite and scheelite by hydrometallurgical treatment. Intermediates such as tungsten trioxide, tungsten blue oxide, tungstic acid, and ammonium metatungstate can be derived from APT by thermal decomposition or chemical attack. Tungsten metal powder is produced through the hydrogen reduction of high-purity tungsten oxides, and tungsten carbide powder is produced by the reaction of tungsten powder and carbon black powder at 1300-1700℃ in a hydrogen atmosphere. Tungsten scrap can be divided into hard and soft scrap based on shape (bulk or powder). It can also be divided into new scrap generated during the production of tungsten-bearing goods and old scrap collected at the end of life. Recycling technologies for tungsten can be divided into four main groups: direct, chemical, and semi-direct recycling, and melting metallurgy. In this review, the current status of tungsten smelting and recycling technologies is discussed.

• 수산해양기술연구
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• 제26권4호
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• pp.333-340
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• 1990

평판형과 만곡형전개판 주위에서의 유체특성을 파악하기 위하여 회유수조에서 수조기포법에 의한 하시화실험을 유속 0.05 및 0.1m/sec, 영각과 타임라인에 대해서 실시하였다. 그 결과를 요약하면 다음과 같다. 1. 만곡형전개판에서의 유선은 영각 20。까지는 균일한 분포를 이루다가 영각 25。에서 후면에 인접한 유선이 익현장의 1/2지점에서부터 작은 과가 발생되기 시작하고, 영각 30。에서는 익현자의 1.3지접에서 박리가 시작되며 인접한 유선은 전개판의 후면쪽으로 휘어들어가고, 그리고 영각 35。이상에서는 전연에서부터 박리가 시작되며 영각이 증가할수록 박리층이 증가하는 것으로 나타났다. 2. 평판형전개판에서는 영각 20。부터 전연에서 과와 박리가 발생하며, 박리층은 만곡형과 마찬가지로 영각에 비례하는 것으로 나타났다. 3. 후연에서 발생한 과의 크기가 전연의 것보다 약 2~3배 큰 것으로 나타났다. 4. 전개판의 후연에서 유선은 양 전개판 모두 전개판의 방향과 같은 방향으로 흐르다가 점차 유체흐름과 같은 방향이 되는 것으로 나타났다. 5. 전개판 전후면에서의 유속차는 영각 0。~30。에서 점차 증가하다가 영각 35。이상에서는 그 차가 비슷하게 나타났다. 6. 영각 20~30。에서 전후면의 유속차는 만곡형의 경우 후면의 유속이 전면보다 약 1.4~1.5배 빠르게 나타났으며, 평판형은 약 1.2배 빠르게 나타났다.

• Mycobiology
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• 제41권1호
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• pp.47-55
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• 2013

Rhizoctonia solani, Fusarium solani, F. oxysporum, and Macrophomina phaseolina were found to be associated with root rott and wilt symptoms of faba bean plants collected from different fieldes in New Valley governorate, Egypt. All the obtained isolates were able to attack faba bean plants (cv. Giza 40) causing damping-off and root rot/wilt diseases. R. solani isolates 2 and 5, F. solani isolate 8, F. oxysporum isolate 12 and M. phaseolina isolate 14 were the more virulent ones in the pathogenicity tests. Biocontrol agents (Trichoderma viride and Bacillus megaterium) and chemical inducers (salicylic acid [SA] and hydrogen peroxide) individually or in combination were examined for biological control of damping-off and root rot/wilt and growth promoting of faba bean plants in vitro and in vivo. Both antagonistic biocontrol agents and chemical inducers either individually or in combination inhibited growth of the tested pathogenic fungi. Biocontrol agents combined with chemical inducers recorded the highest inhibited growth especially in case SA + T. viride and SA + B. megaterium. Under green house and field conditions, all treatments significantly reduced damping-off and root rot/wilt severity and increased of survival plants. Also, these treatments increased fresh and weights of the survival plants in pots compared with control. The combination between biocontrol agents and chemical inducers were more effective than used of them individually and SA + T. viride was the best treatment in this respect. Also, under field conditions, all these treatments significantly increased growth parameters (plant height and number of branches per plant) and yield components (number of pods per plant and number of seeds per plant, weight of 100 seeds and total yield per feddan) and protein content in both seasons (2010~2011 and 2011~2012). Faba bean seeds soaked in SA + T. viride and SA + B. megaterium were recorded the highest growth parameters and yield components. Generally, the combination between biocontrol agents and chemical inducers recorded the best results for controlling damping-off and root rot/wilt diseases in greenhouse and field with addition improved plant growth and increased yield components in field.

• Molecules and Cells
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• 제37권4호
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• pp.322-329
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• 2014

N-acetylglucosamine kinase (GlcNAc kinase or NAGK; EC 2.7.1.59) is highly expressed and plays a critical role in the development of dendrites in brain neurons. In this study, the authors conducted structure-function analysis to verify the previously proposed 3D model structure of GlcNAc/ATP-bound NAGK. Three point NAGK mutants with different substrate binding capacities and reaction velocities were produced. Wild-type (WT) NAGK showed strong substrate preference for GlcNAc. Conversion of Cys143, which does not make direct hydrogen bonds with GlcNAc, to Ser (i.e., C143S) had the least affect on the enzymatic activity of NAGK. Conversion of Asn36, which plays a role in domain closure by making a hydrogen bond with GlcNAc, to Ala (i.e., N36A) mildly reduced NAGK enzyme activity. Conversion of Asp107, which makes hydrogen bonds with GlcNAc and would act as a proton acceptor during nucleophilic attack on the ${\gamma}$-phosphate of ATP, to Ala (i.e., D107A), caused a total loss in enzyme activity. The overexpression of EGFP-tagged WT or any of the mutant NAGKs in rat hippocampal neurons (DIV 5-9) increased dendritic architectural complexity. Finally, the overexpression of the small, but not of the large, domain of NAGK resulted in dendrite degeneration. Our data show the effect of structure on the functional aspects of NAGK, and in particular, that the small domain of NAGK, and not its NAGK kinase activity, plays a critical role in the upregulation of dendritogenesis.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.