• Bulletin of the Korean Chemical Society
• /
• v.20 no.9
• /
• pp.1017-1020
• /
• 1999

The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.11
• /
• pp.1198-1202
• /
• 1998

Aminolysis of aryl thiol-2-furoates and thiol-2-thiophenates with benzylainines are investigated in acetonitrile at 50.0 ℃. Relatively large selectivity parameters, ρx(βx), ρz(βx) and ρxz (> 0) together with the valid reactivity-selectivity principle are consistent with a stepwise acyl transfer mechanism with rate-limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T±. The first-order kinetics with respect to the benzylamine concentration and the relatively large secondary kinetic isotope effect involving deuterated benzylamine nucleophiles suggest a four-center type transition state in which concurrent leaving group departure and proton transfer are involved.

• Bulletin of the Korean Chemical Society
• /
• v.5 no.5
• /
• pp.207-208
• /
• 1984

The tris(hydroxymethyl)aminomethane (Tris)-catalyzed hydrolysis of p-nitrotrifluoroacetanilide was kinetically studied. On the contrary to the previously reported results (R. M. Pollack and T. C.Dumsha, J. Am. Chem. Soc., 1973, 95, 4463), the dependence of the rate on [Tris] consists of an initial curve portion and a subsequent linear increase. This indicates that erroneous conclusions were made in the reported work due to the insufficient amount of data. The initial portions of the rate[Tris] profiles are attributed to the catalyzed breakdown of the tetrahedral intermediate, and the linear portions to the general base-catalyzed water attack at the substrate.

• Journal of Integrative Natural Science
• /
• v.7 no.3
• /
• pp.149-158
• /
• 2014

The crystal structure of the title compounds with both coumarin and sulfonamide moieties were examined. These two groups have very special for their pharmaceutical and medicinal properties have been determined from single crystal X-ray diffraction data. In the title compound crystallizes in the monoclinic space group $P2_1/c$ with unit cell dimension a=$8.5775(4){{\AA}$, b=$24.9943(13){\AA}$ and c=$13.7319(7){\AA}$ [alpha & gamma=$90^{\circ}$ beta=$103.558(2)^{\circ}$]. In the structure The S1 atom shows a distorted tetrahedral geometry, with O1-S1-O2 [$121.08(1)^{\circ}$] and N1-S1-C5 [$105.85(1)^{\circ}$] angles deviating from ideal tetrahedral values are attributed to the Thrope-Ingold effect. The sum of bond angles around N1 ($354.9^{\circ}$) indicates that N1 is in $sp^2$ hybridization. The Pyridine ring adopts boat conformation and pyran rings adopt a sofa conformation. Crystal structure is stabilized by C-H...O intra molecular hydrogen bond interactions.

• Journal of the Korean Chemical Society
• /
• v.56 no.6
• /
• pp.679-691
• /
• 2012

New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

• Journal of the Korean Applied Science and Technology
• /
• v.8 no.1
• /
• pp.59-67
• /
• 1991

The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
• /
• 2001.06a
• /
• pp.1181-1181
• /
• 2001

Robinson with ${coworkers}^{1}$ have introduced two-state outer-neighbor bonding model to explain the anomalies of water. The studies on the properties of water as a function of temperature and pressure revealed that, unlike other ideas, all $H_2O$ molecules in liquid are tetrabonded. On the average they are forming two different bonding types. One type is the regular tetrahedral water-water bonding similar to that found in the ordinary ice Ih, whereas the other is a more dense nonregular tetrahedral bonding similar to that appearing in the ice II. The transformation between these two bonding forms is evidenced by FT-NIR experiment. The FT-NIR measurements were done for liquid water in the temperature range from $20^{\circ}C$ up to $80^{\circ}C$ in a wide extent of frequencies: 12 000 - 4000 $cm^{-1}$ /. Temperature dependent variations in the volume fraction of these two structures are directly related to the spectral changes. The absorbance variations are explored by means of the two-dimensional correlation spectroscopy (2DCOS), principal component analysis (PCA), curve fitting and second derivatives. The presence of the isosbestic points in a range of the combination and overtone transitions indicates that the experimental spectra are a superposition of two temperature independent components. One component of diminishing intensity with temperature increase, is assigned to a stronger hydrogen bonds occurred in the Ih type, whereas the second component showing an opposite behavior, one can attribute to a weaker H-bonds characteristic for the II type. The understanding of the hydrogen bonding network in the liquid water is very important in interpretation of the interaction between water and protein chain. The two-state model of water surrounding the protein surface could advance an understanding of the hydration process.

• Journal of Korean Ophthalmic Optics Society
• /
• v.3 no.1
• /
• pp.223-228
• /
• 1998

Glass films of $SiO_2-TiO_2-M_xO_y$ (M = Co, Cr or Cu) have been prepared on soda-lime-silica slide glasses by the chemical solution method using a spin-coating technique. Commercially available tetraethyl orthosilicate, titanium trichloride, and cobalt-, chromium- and copper-nitrates were used as starting materials. No crystalline segregations of $Co_3O_4$, $Cr_2O_3$ and CuO were observed by X-ray diffraction ${\theta}-2{\theta}$ scans. From the optical transmission analysis, cobalt existed as $ Co^{2+}$ in tetrahedral coordination, chromium as $Cr^{6+}$ in tetrahedral symmetry and copper as $Cu^{2+}$ in octahedral coordination. Films with a crack-free and no texture exhibited homogeneous interfaces between the films and the substrates along the cross-section.

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.38 no.1
• /
• pp.63-70
• /
• 2014

In the present study, CFD simulations were conducted for investigating intra-aneurysmal flow characteristics with different stent porosities ($C_{\alpha}$ = 80%, 74%, and 64%), and the simulation results were compared with experimental data. Using a quadratic tetrahedral element-based finite element scheme, we estimated velocity fields and wall shear stress. The intra-aneurysmal velocity reduction ratios obtained via simulation agree well with published experimental data. It was found that a stent with a porosity of 80%, which is highest in the present study, is able to effectively reduce flow into the aneurysm, which causes intra-aneurysmal stasis, and that stents with lower porosities afford only incremental benefits in reducing inflow to an aneurysm.

• Tribology and Lubricants
• /
• v.35 no.6
• /
• pp.362-368
• /
• 2019

In this study, mechanical and tribological properties were investigated by varying the process temperature (50, 100, 125 and 150℃) to reduce internal stress. The internal stress reduction by thermal dissociation ta-C coating film with increasing temperature is confirmed through the curvature radius of the ta-C coating according to the temperature of the SUS plate. As the coating temperature increased, the mechanical properties (hardness, modulus, toughness) deteriorated, which is in agreement with the Raman analysis results. As the temperature increased, the sp² phase ratio increased owing to the dissociation of the sp³ phase. The friction and wear properties are related to the process temperature during ta-C coating. Low friction and wear properties are observed in high hardness samples manufactured at 50℃, and wear resistance properties decreased with increasing temperature. The contact area is expected to increase owing to the decrease of hardness(72 GPa to 39 GPa) and fracture toughness with increasing temperature which accelerated wear because of the debris generated. It was confirmed that at process temperature of over than 100℃, the bond structure of the carbon film changed, and the effect of excellent internal stress was reduced. However, the wear resistance simultaneously decreased owing to the reduction in fracture toughness. Therefore, in order to increase industrial utilization, optimum temperature conditions that reduce internal stress and retain mechanical properties.