• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.483-488
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• 2014

The nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $35.0^{\circ}C$. The Hammett and Bronsted plots with X in the nucleophiles for both substrates exhibit biphasic concave upwards with a break region between X = 3-Me and H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are negative with 8 while positive with 10 despite the same free energy correlations with X for both substrates. A stepwise mechanism with a rate-limiting bond formation is proposed with 8, whereas a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed with 10 based on the sign of ${\rho}_{XY}$, negative and positive with 8 and 10, respectively. A frontside nucleophilic attack is proposed with strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values while a backside attack is proposed with weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$ for both substrates.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2009-2014
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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.

• Carbon letters
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• v.5 no.3
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• pp.108-112
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• 2004

Effect of silicon infiltration on the bend and tensile strength of 2D cross-ply carbon-carbon composites are studied. It is observed that bend strength higher than tensile strength in both types of composite is due to the different mode of fracture and loading direction. After silicon infiltrations bend and tensile strength suddenly decreases of carbon-carbon composites. This is due to the fact that, after silicon infiltration, silicon in the immediate vicinity of carbon forms the strong bond between carbon and silicon by formation silicon carbide and un-reacted silicon as free silicon. Therefore, these composites consist of three components carbon, silicon carbide and silicon. Due to mismatch between these three components secondary cracks developed and these cracks propagate from $90^{\circ}$ oriented plies to $0^{\circ}$ oriented plies by damaging the fibers (i.e., in-situ fiber damages). Hence, secondary cracks and in-situ fiber damages are responsible for degradation of mechanical properties of carbon-carbon composites after silicon infiltration which is revealed by microstructure investigation study by scanning electron microscope.

• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Korean Journal of Metals and Materials
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• v.48 no.5
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• pp.401-409
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• 2010

This study was performed to develop an antibacterial film that can be dried at room temperature. A nanosized TiO$_2$ particle-dispersed solution was prepared by the hydrothermal treatment of peroxo-titanic acid at 160${^{\circ}C}$ for 4h. The binder was synthesized through the hydrolysis and condensation reactions of TEOS (10cc) and GPTS (3.5cc) in the mixture of H$_2$O (30cc) and EtOH (30cc). The synthesized binder was mixed with 0.1 M of TiO$_2$ solution in a volume ratio of binder/TiO$_2$ solution=0.25~0.5. The glass substrate was coated after using the dip coating method, which was then followed by drying for over 2h at room temperature. Although the TiO$_2$ particles did not chemically-bond to the binder, the coating layer strongly adhered to the substrate and displayed good antibacterial properties.

• Electrical & Electronic Materials
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• v.16 no.9
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• pp.63.2-64
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• 2003

Epitaxial yttrium-stabilized HfO$_2$ thin films were deposited on p-type (100) Si substrates by pulsed laser deposition at a relatively lower substrate temperature of 550. Transmission electron microscopy observation revealed a fixed orientation relationship between the epitaxial film and Si; that is, (100)Si.(100)HfO$_2$ and [001]Si/[001]HfO$_2$. The film/Si interface is not atomically flat, suggesting possible interfacial reaction and diffusion, X-ray photoelectron spectrum analysis also revealed the interfacial reaction and diffusion evidenced by Hf silicate and Hf-Si bond formation at the interface. The epitaxial growth of the yttrium stabilized HfO$_2$ thin film on bare Si is via a direct growth mechanism without involoving the reaction between Hf atoms and SiO$_2$ layer. High-frequency capacitance-voltage measurement on an as-grown 40-A yttrium-stabilized HfO$_2$ epitaxial film yielded an dielectric constant of about 14 and equivalent oxide thickness to SiO$_2$ of 12 A. The leakage current density is 7.0${\times}$ 10e-2 A/$\textrm{cm}^2$ at 1V gate bias voltage.

• Journal of Microbiology and Biotechnology
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• v.27 no.12
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• pp.2190-2198
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• 2017

Thermoactinomyces sp. strain YT06 was isolated from poultry compost and observed to degrade integral chicken feathers completely at $60^{\circ}C$, resulting in the formation of 3.24 mg/ml of free amino acids from 50 ml of culture containing 10 g/l chicken feathers. Strain YT06 could grow and secrete keratinase using feather as the only carbon and nitrogen sources without other supplement, but complementation of 10 g/l sucrose and 4 g/l $NaNO_3$ increased the production of the keratinolytic enzyme. The maximum protease activity obtained was 110 U/ml and for keratinase was 42 U/ml. The keratinase maintained active status over a broad pH (pH 8-11) and temperature ($60-75^{\circ}C$). It was inhibited by serine protease inhibitors and most metal ions; however, it could be stimulated by $Mn^{2+}$ and the surfactant Tween-20. A reductive agent (${\beta}$-mercaptoethanol) was observed to cleave the disulfide bond of keratin and improve the access of the enzyme to the keratinaceous substrate. Zymogram analysis showed that strain YT06 primarily secreted keratinase with a molecular mass of approximately 35 kDa. The active band was assessed by MALDI-TOF mass spectrometry and was observed to be completely identical to an alkaline serine protease from Thermoactinomyces sp. Gus2-1. Thermoactinomyces sp. strain YT06 shows great potential as a novel candidate in enzymatic processing of hard-to-degrade proteins into high-value products, such as keratinous wastes.

• Applied Biological Chemistry
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• v.31 no.4
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• pp.361-370
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• 1988

To investigate the interaction between whey and soybean protein, thermal changes of component proteins were analyzed by column chromatography and gel electrophoresis. In the Sephadex G-200 chromatography of the mixture treated at above $80^{\circ}C$, the amount of low molecular weight proteins and high molecular aggregates were increased. This implicated that dissociation of 1ls globulin into subunits and the formation of soluble aggregates between these subunits and whey proteins that contain thiol and disulfide groups. These interaction between soy proteins and ${\beta}-lactoglobulin$, ${\alpha}-lactalbumin$, and proteose-peptone 3 were confirmed by gel electrophoresis. Bovine serum albumin, Immunoglobulin-G(H), Lactoferrin, 1ls-subunits(basic and acidic), and subunit of 7s globulin were also considered to interact each other depending on the condition of the salt solutions.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.199-199
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• 2011

The addition of a carbanion to ${\yen}{\acute{a}}{\yen}{\hat{a}}$-unsaturated carbonyl compounds is of importance in the C-C bond formation reactions for modern pharmaceuticals and organic synthesis. Recently, heterogeneous asymmetric catalysis became more attractive area of research because of the easy recovery and separation of the catalyst from the reaction system. Most of synthetic methods for heterogeneous catalysts were grafting or immobilization of homogeneous catalyst onto the solid supports. Trans-1,2-Diaminocyclohexane(DACH) and L-proline ligands have been enormously used as chiral ligands in several catalytic transformation under homogenous conditions. Our group prepared l-proline functionalized mesoporous silica was synthesized under acidic condition using a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer template (EO20PO70EO20, Pluronic P-123, BASF). Furthermore, we successfully directly synthesized trans-1,2 diaminocyclohexane functionalized mesoporous silica by using microwave method. The direct functionalization of chiral ligand into the framework of mesoporous materials is expected to be useful for the heterogeneous asymmetric catalysis. So, we adopt the direct synthesis of chiral ligand functionalized mesoporous silica by using thermal and microwave irradiation. Then, chiral ligand functionalized mesoporous silicas were applied to enantioselective asymmetric catalytic reactions.

• Journal of the Korean Ceramic Society
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• v.41 no.1
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• pp.13-18
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• 2004

$La_{0.5}Sr_{0.5}CoO_3$ (LSCO) electrodes were prepared on ferroelectric $Sr_{0.9}Bi_{2.1}Ta_2O_9$(SBT) thin films by spin coating method using photosensitive sol-gel solution. Self-patterning technique of photosensitive sol-gel solution has advantages such as simple manufacturing process compared to photoresist/dry etching process. Lanthanum(III) 2-methoxyethoxide, Stronitium diethoxide. Cobalu(II)2-methoxyethoxide were used as starting materials for LSCO electrode. UV irradiation on LSCO thin films lead to decrease solubility by M-O-M bond formation and the solubility difference allows us to obtain self-patternine. There was little composition change of the LSCO thin films between before leaching and after leaching in 2-methoxyethanol. The lowest resistivity of LSCO thin films deposited on $SiO_2$/Si substrate was $1.1{\times}10^{-2}{\Omega}cm$ when the thin film was ennealed at $740^{\circ}C$. The values of Pr/Ps and 2Pr of LSCO/SBT/Pt capacitor on the applied voltage of 5V were 0.51, 8.89 ${\mu}C/cm^2$, respectively.