• Analytical Science and Technology
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• v.35 no.1
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• pp.24-31
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• 2022

Herein, we present a simple, precise, accurate, and ultra-sensitive spectrofluorimetric method for estimation of clozapine (CLZ) in tablets and human plasma was developed and then validated. A highly fluorescent brown-yellowish fluorophore was formed (λ_ex=469 nm, λ_emi=540 nm) as a nucleophilic substitution reaction occurred between CLZ and 4-chloro-7-nitro-2,1,3-benzoxadiazole (NBD-Cl) in alkaline mcllavine buffer (pH 9.0). Optimum values of experimental parameters were carefully determined and optimized. The calibration curve was rectilinear over the concentration range of 80-900 ng mL^-1 with a linear correlation coefficient (r=0.9984). The LOD and LOQ were determined to be 14 ng mL^-1 and 42 ng mL^-1, respectively. The proposed approach has been used successfully to quantification of Clozapine in its commercial formulations and human plasma.

• YAKHAK HOEJI
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• v.49 no.4
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• pp.255-259
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• 2005

Financial standing of National Health Insurance has been experiencing a grave deterioration during the last 4-5 years, and the yearly amount paid by the insurance for drug expense rose up to 4 trillion won recently. Furthermore, the ratio of drug expenses in the total expenditure of the insurance reached about $25\%$, showing the tendency to be levelled off. As a measure to improve the financial deterioration of the insurance and to encourage generic substitution among the health professionals, we compared pharmacokinetic parameters of brand name drug (Lamisil) and generic drug (Muzonal) containing terbinafine HCl in healthy volunteers. The area under the curve (AUC) of the two drugs showed $2220.4\pm784.7\;and\;2143.1\pm861.6hr{\cdot}ng/ml$ in the corresponding order and no statistically significant difference was identified. The peak concentration $(C_{max})$ of the generic drug demonstrated $566.6\pm246.2 ng/ml$ compared to $550.8\pm204.0$ of brand name drug, which was not significantly different either. Time to reach peak concentration showed about 6 minutes difference between the drugs, which has no clinical significance to the treatment of dermatomycosis and dermatophytosis.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.225-230
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• 2014

A kinetic study on nucleophilic substitution reactions of 4-nitrophenyl X-substituted-benzoates (7a-i) with EtOK in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of pseudo-first-order rate constants ($k_{obsd}$) vs. [EtOK] curve upward. Dissection of $k_{obsd}$ into the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOK (i.e., $k_{EtO^-}$ and $k_{EtOK}$, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. Hammett plots for the reactions of 7a-i with the dissociated $EtO^-$ and ion-paired EtOK exhibit excellent linear correlations with ${\rho}_X$ = 3.00 and 2.47, respectively. The reactions have been suggested to proceed through a stepwise mechanism in which departure of the leaving-group occurs after the RDS. The correlation of the $k_{EtOK}/k_{EtO^-}$ ratio with the ${\sigma}_X$ constants exhibits excellent linearity with a slope of -0.53. It is concluded that the ion-paired EtOK catalyzes the reaction by increasing the electrophilicity of the reaction center rather than by enhancing the nucleofugality of the leaving group.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.31-36
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• 1989

The second-order rate constants for the nucleophilic substitution reactions of para-substituted benzyl nitrates with para-substituted anilines in acetonitrile were conductometrically determined. Hammett ${\rho}$x and ${\rho}$y values and Bronsted ${\beta}$ values were obtained from these kinetic data. The reactions of Benzyl nitrates with the series of anilines showed linear Hammett plots with negative slopes. For the change of substituents in the benzyl nitrates, nonlinear Hammett plots with a concave upwards curve were obtained. We applied the potential energy surface and the quantum mechanical models in order to examine the transition state variations caused by changes in substituents on the nucleophile and the substrate. The results showed that the reaction was proceeded via the $S_{N}2$-type reaction mechanism in which the extent of bond-formation was greatly changed depending on the property of the substituents in substrate.

• Journal of the Korean Ceramic Society
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• v.31 no.12
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• pp.1577-1587
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• 1994

TiO2 thin films with the substitution of oxygen with nitrogen were deposited on silicon substrate by metalorganic chemical vapor deposition (MOCVD) using Ti(OCH(CH3)2)4 (titanium tetraisopropoxide, TTIP) and N2O as source materials. X-ray diffraction (XRD) results indicated that the crystal structure of the deposited thin films was anatase TiO2 with only (101) plane observed at the deposition temperatures of 36$0^{\circ}C$ and 38$0^{\circ}C$, and with (101) and (200) plane at above 40$0^{\circ}C$. Raman spectroscopic results indicated that the crystal structure was anatase TiO2 in accordance with the XRD results without any rutile, fcc TiN, or hcp TiN structure. No fundamental difference was observed with temperature increase, but the peak intensity at 194.5 cm-1 increased with strong intensity at 143.0 cm-1 for all samples. The crystalline size of the films varied from 49.2 nm to 63.9 nm with increasing temperature as determined by slow-scan XRD experiments. The refractive index of the films increased from 2.40 to 2.55 as temperature increased. X-ray photoelectron spectroscopy (XPS) study showed only Ti 2s, Ti 2p, C 1s, O 1s and O 2s peaks at the surface of the film. The composition of the surface was estimated to be TiO1.98 from the quatitative analysis. In the bulk of the film Ti 2s, Ti 2p, O 1s, O 2s, N 1s and N 2s were detected, and Ti-N bonding was observed due to the substitution of oxygen with nitrogen. A satellite structure was observed in the Ti 2p due to the Ti-N bonding, and the composition of titanium nitride was determined to be about TiN1.0 from the position of the binding energy of Ti-N 2p3/2 and the quatitative analysis. The spectrum of Ti 2p energy level could be the sum of a 4, 5, or 6 Gaussian curve reconstruction, and the case of the sum of the 6 Gaussian curve reconstruction was physically most meaningful. From the results of Auger electron spectroscopy (AES), it was known that the composition was not varied significantly throughout the whole thickness of the film, and silicon oxide was not observed at the interface between the film and the substrate. The composition of the film was possible (TiO2)1-x.(TiN)x or TiO2-2xNx and in this experimental condition x was found to be about 0.21-0.16.

• Journal of the Korea Concrete Institute
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• v.25 no.4
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• pp.439-446
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• 2013

The objective of this study is to evaluate the workability and various mechanical properties of heavyweight magnetite concrete and examine the reliability of the design equations specified in code provisions. The main parameters investigated were the water-to-cement ratio and substitution level of normal-weight coarse aggregate (granite) for magnetite. The oven-dried unit weight of concrete tested ranged between 2446 and $3426kg/m^3$. The measured mechanical properties included compressive strength development, stress-strain curve, splitting tensile strength, moduli of elasticity and rupture, and bond stress-slip relationship of concrete. Test results revealed that the initial slump of heavyweight magnetite concrete increased as the substitution level of normal-weight coarse aggregate increases. The substitution level of normal-weight coarse aggregate had little influence on the compressive strength and tensile resistance capacity of heavyweight concrete, while it significantly affected the modulus of elasticity and stress-strain curves of such concrete. The design equations of ACI 349-06 and CEB-FIP provisions mostly conservatively predicted the mechanical properties of heavyweight magnetite concrete, but the empirical equations for modulus of elasticity and splitting tensile strength need to be modified considering the unit weight of concrete.

• Journal of Magnetics
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• v.11 no.1
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• pp.36-42
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• 2006

In this report, we demonstrate a comprehensive analysis of the effects of Au addition on the microstructure and magnetic properties of $Fe_{73.5}Si_{13.5}B_{9}Nb_{3}Au_1$ Finemet-type alloy. It was found that the as-quenched alloys were the amorphous state and turned into nanocrystalline state under heat treatments. The DSC analysis indicates that the sharply exothermal peak corresponding to the crystallization of the $\alpha-Fe(Si)$ was observed at $547-579^{\circ}C$ depending on the heating rates, which is little higher than that of original Finemet (542-$570{^{\circ}C}$, respectively). Besides, the thermomagnetic result confirmed that the full substitution of Cu by Au with the single phase structure in the M(T) curve along cooling cycle. Ultrasoft magnetic properties of the nanocrystallized samples were significantly enhanced by the proper annealing such as the increase of permeability and the decrease of the coercivity. The optimum annealing condition was found at the annealing temperature of $540^{\circ}C$ and the increase of the annealing time up to 90 min.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1722-1726
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• 2013

A kinetic study on nucleophilic substitution reactions of phenyl Y-substituted-phenyl carbonates (5a-5j) with ethylamine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ is reported. The plots of $k_{obsd}$ vs. [amine] are linear for the reactions of substrates possessing a strong electron-withdrawing group (EWG) but curve upward for those of substrates bearing a weak EWG, indicating that the electronic nature of the substituent Y in the leaving group governs the reaction mechanism. The reactions have been concluded to proceed through a stepwise mechanism with one or two intermediates (a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$) depending on the nature of the substituent Y. Analysis of Bronsted-type plots and dissection of $k_{obsd}$ into microscopic rate constants have revealed that the reactions of substrates possessing a strong EWG (e.g., 5a-5f) proceed through $T^{\pm}$ with its formation being the rate-determining step, while those of substrates bearing a weak EWG (e.g., 5g-5j) proceed through $T^{\pm}$ and $T^-$.

• Journal of Photoscience
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• v.7 no.2
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• pp.67-71
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• 2000

A quantum-chemical investigation on the conformations and electronic properties of trans(diphenyl-diheterocyclic) ethenes(t-PHEs) as building block for fully $\pi$-conjuated polymer are performed in order to display the effects of heterocyclic ring substitution. Structures for the molecules, t-PHEs were fully optimized by using semiempirical AM1, PM3 methods, and ab initio HF methods, with 6-31G basic set. The potential energy curves with respect to the change of single are obtained by using ab initio HF/6-31G basic set. The curves are not similar shapes in the molecules with respect to heterocyclic rings. It is shown that the steric repulsion interactions between phenyl ring and heterocyclic ring are subjected to different type with the respect to each heterocyclic ring. Electronic properties of the molecules were molecules were obtained by applying the optimized structures and selected geometries to the extended Huckel method. To investigate the change of HOMO-LUMO gap with respedt to the torsion angle, we select the optimized structures. By using the results, the dependency of conjugation for the energy gaps is analyzed. For t-PHE the energy gap increase up to 0.52 eV compared with its planar structure. In the cases of t-PHE and t-PHE, the energy gap increase by 1.29 and 1.15 eV, respectively, compared with its planar structure.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2130-2134
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl isonicotinate (7) with a series of cyclic secondary amines in MeCN. The plots of $k_{obsd}$ vs. [amine] curve upward for the reactions with weakly basic amines (e.g., morpholine, 1-(2-hydroxyethyl)piperazine, and piperazine) but are linear for those with strongly basic amines (e.g., piperidine and 3-methylpiperidine). The curved plots for the reactions with the weakly basic amines are typical for reactions reported previously to proceed through uncatalyzed and catalyzed routes with two intermediates (e.g., a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$). In contrast, the linear plots for the reactions with the strongly basic amines indicate that the catalytic route (i.e., the deprotonation process to yield $T^-$ from $T^{\pm}$ by a second amine molecule) is absent. The Br${\o}$nsted-type plots for $Kk_2$ and $Kk_3$ (i.e., the rate constants for the uncatalyzed and catalyzed routes, respectively) exhibit excellent linear correlations with ${\beta}_{nuc}$ = 0.99 and 0.69, respectively. The effect of amine basicity on the reaction mechanism is discussed in detail.