• Bulletin of the Korean Chemical Society
• /
• 제31권9호
• /
• pp.2483-2487
• /
• 2010

Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

• 대한화학회지
• /
• 제33권1호
• /
• pp.31-36
• /
• 1989

순수한 아세토니트릴용매에서 질산파라-치환 벤질과 파라-치환 아닐린간의 친핵성 치환반응에 대한 2차반응속도상수를 전기전도도법으로 구하여 Hammett ${\rho}$x와 ${\rho}$y값 및 Bronsted ${\beta}$값을 계산하였다. 이때 아닐린의 치환기 변화에 따르는 ${\rho}$x는 음의 값으로 주어졌으며 기질의 치환기에 따라서는 U자 모양의 비직선성 Hammett 도시가 얻어졌다. 포텐셜에너지표면 및 양자역학적 모형을 적용하여 치환기 변화에 따른 천이상태 구조의 변화를 고찰하여 본 결과 본 반응은 기질의 치환기의 성질에 따라 결합형성의 정도가 크게 변화하는 $S_{N}2$ 반응 메카니즘으로 진행함을 알 수 있었다.

• Transactions on Electrical and Electronic Materials
• /
• 제3권3호
• /
• pp.21-24
• /
• 2002

Two kinds of $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$, the sintering samples and zone melting samples, were heat-treated under pure Ar at 950$^{circ}C$. The substitution of Nd ion for Ba ion in the $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ before and after the heat treatment was investigated by XRD. In order to confirm the effects of the heat treatment, the Tc and Jc of samples with/without the heat treatment under Ar were comparatively studied. $Nd_{1+X}Ba_{2-X}Cu_3O_{7-{\delta}}$ samples were oxygenated under pure oxygen at $300^{circ}C$. From the XRD pattern it was found that the sample with x<0.4 was transferred from tetragonal phase to orthorhombic phase after the oxygenation, while the sample with x>0.4 did not show the phase transition even after a long time oxygenation. Therefore, the low oxygen partial pressure (Ar+1 % O$_2$) was used for the ambient atmosphere of the zone-melting samples, which could reduce the melting temperature and depress the substitution of Nd for Ba. After the improvement in the zone-melting process, the Jc value was increased to 2 x $10^4$A/$cm^2$ (0 T, 78 K). The particle orientation and the structure of zone-melted NdBaCuO were studied by the XRD and SEM analysis.

• 한국재료학회지
• /
• 제29권9호
• /
• pp.559-566
• /
• 2019

$Lu(Nb,Ta)O_4:Eu^{3+}$ powders are synthesized by a solid-state reaction process using LiCl and $Li_2SO_4$ fluxes. The photoluminescence (PL) excitation spectra of the synthesized powders consist of broad bands at approximately 270 nm and sharp peaks in the near ultraviolet region, which are assigned to the $Nb^{5+}-O^{2-}$ charge transfer of $[NbO_4]^{3-}$ niobates and the f-f transition of $Eu^{3+}$, respectively. The PL emission spectra exhibit red peaks assigned to the $^5D_0{\rightarrow}^7F_J$ transitions of $Eu^{3+}$. The strongest peak is obtained at 614 nm ($^5D_0{\rightarrow}^7F_2$), indicating that the $Eu^{3+}$ ions are incorporated into the $Lu^{3+}$ asymmetric sites. The addition of fluxes causes the increase in emission intensity, and $Li_2SO_4$ flux is more effective for enhancement in emission intensity than is LiCl flux. The substitution of $Ta^{5+}$ for $Nb^{5+}$ results in an increase or decrease in the emission intensity of $LuNb_{1-x}Ta_xO_4:Eu^{3+}$ powders, depending on amount and kind of flux. The findings are explained using particle morphology, modification of the $[NbO_4]^{3-}$ structure, formation of substructure of $LuTaO_4$, and change in the crystal field surrounding the $Eu^{3+}$ ions.

• 한국세라믹학회지
• /
• 제40권1호
• /
• pp.37-45
• /
• 2003

$BaTiO_3$의 Ba 자리에 Ca, Ti 자리에 Zr을 첨가한 $(B a_{1-x}Ca_x)(Ti_{0.96-y}Zr_{y}Sn_{0.04})O_3$ $(0.15 {\leq} x{\leq}0.20,\; 0.09{\leq}y{\leq}$0.14) 조성에 2차상 형성을 유도하여 복합체를 만든 후 유전 및 소결 특성을 조사하였다. Ca량이 15mol% 이상 첨가됨에 따라 $CaTiO_3$를 주성분으로 하는 2차상이 석출하여 복합체가 형성되었으며, Ca량의 증가에 따라 2차상 분율이 증가하였다. Ca량의 증가는 큐리 온도를 mol%당 $1.7^{\circ}C$ 감소시키며, 저유전율 2차상의 영향으로 Ca량 증가에 따라 최대 유전율은 mol%당 200 감소하였다. Zr 첨가는 큐리온도를 mol%당 $10^{\circ}C$ 감소시키며, 확산형 상전이 현상을 증가시켜 최대 유전율을 217 감소시켰다. 2차상의 증가에 의하여 비정상 입성장이 억제되어 소결밀도, 내전압 특성이 향상되었으며, Zr 첨가에 의하여 커패시턴스의 온도 안정성을 제어하여 EIA 규격을 만족하는 고압, 고유전율 Y5U 콘덴서 조성을 개발하였다.

• 한국결정성장학회지
• /
• 제7권2호
• /
• pp.253-258
• /
• 1997

반도체화 첨가제인 $Y_2O_3$와 $Nb_2O_5$ 첨가랑 변화에 따른 PTCR $BaTiO_3$ 세라믹스의 결정구조 해석과 상전이 특성을 연구하기 위하여 ($Ba_{0.85}Ca_{0.15})TiO_3$ ＋ X m/o $Nb_2O_5$(Y m/o $Y_2O_3$) ＋ 0.08 w/o $Mn(NO_3)_2$ㆍ$6H_2O$ ＋ 0.25 w/o $SiO_2$ 계에서 X는 0.1 ~ 0.4로 Y는 0.2 ~ 0.4로 각각 변화시켜 실험을 수행하였다. $Nb_2O_5$의 첨가시 B-site 치환에 따라서 격자상수가 선형적으로 변화하다가 0.3 mol% 이상 치환할 경우 c 축의 격자상수가 급격히 감소함을 알 수 있었다. 이는 octahedron distortion둥의 원인으로 판단되며, 이러한 격자상수 변화는 상전이 온도 결과와도 잘 일치함을 확인할 수 있었다. 또한 $Y_2O_3$ 첨가의 경우 0.3 mol%가지는 A, B-site를 각각 치환하며 그 이상부터는 A-site 이온을 주로 치환하는 것을 격자상수 변화와 상전이 온도결과를 통해 알 수 있었으며, Rietveld 해석결과 $Y^{3+}$가 A-site 치환시 $Ba^{2＋}$와 $Ca^{2＋}$를 같은 비율로 치환한다는 것을 알 수 있었다.

• Molecules and Cells
• /
• 제19권1호
• /
• pp.114-123
• /
• 2005

Nitropyrene, the predominant nitropolycyclic hydrocarbon found in diesel exhaust, is a mutagenic and tumorigenic environmental pollutant that requires metabolic activation via nitroreduction and ring oxidation. In order to determine the role of ring oxidation in the mutagenicity of 1-nitropyrene, its oxidative metabolites, 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide, were synthesized and their mutation spectra were determined in the coding region of hprt gene of CHO cells by a PCR amplification of reverse-transcribed hprt mRNA, followed by a DNA sequence analysis. A comparison of the two metabolites for mutation frequencies showed that 1-nitropyrene 9,10-oxide was 2-times higher than 1-nitropyrene 4,5-oxide. The mutation spectrum for 1-nitropyrene 4,5-oxide was base substitutions (33/49), one base deletions (11/49) and exon deletions (5/49). In the case of 1-nitropyrene 9,10-oxide, base substitutions (27/50), one base deletions (15/50), and exon deletions (8/50) were observed. Base substitutions were distributed randomly throughout the hprt gene. The majority of the base substitutions in mutant from 1-nitropyrene 4,5-oxide treated cells were $A{\rightarrow}G$ transition (15/33) and $G{\rightarrow}A$ transition (8/33). The predominant base substitution, $A{\rightarrow}G$ transition (11/27) and $G{\rightarrow}A$ transition (8/27), were also observed in mutant from 1-nitropyrene 9,10-oxide treated cells. The mutation at the site of adenine and guanine was consistent with the previous results, where the sites of DNA adduct formed by these compounds were predominant at the sites of purines. A comparison of the mutational patterns between 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide showed that there were no significant differences in the overall mutational spectrum. These results indicate that each oxidative metabolite exhibits an equal contribution to the mutagenicity of 1-nitropyrene, and ring oxidation of 1-nitropyrene is an important metabolic pathway to the formation of significant lethal DNA lesions.

• 한국자기학회지
• /
• 제24권2호
• /
• pp.46-50
• /
• 2014

Sol-gel법을 이용하여 $Fe_3O_4$과 $M_{0.2}Fe_{2.8}O_4$(M =Mn, Ni, Cu) 박막 시료을 만들어 M 치환에 따른 $Fe_3O_4$의 결정구조적 특성 및 양이온 분포를 X-ray diffraction(XRD)과 conversion electron M$\ddot{o}$ssbauer(CEMS) 분광법을 이용하여 조사하였다. CEMS 분광법을 이용하여 Fe 이온의 전하상태와 거동과 초미세 자기적 특성을 분석하였다. $M_{0.2}Fe_{2.8}O_4$(M =Mn, Ni, Cu) 시료들은 $Fe_3O_4$에서와 같이 입방정 스피넬 구조를 나타내었으며, Ni 이온 치환된 시료에서는 격자상수 값이 $Fe_3O_4$에서의 값과 비교하여 감소하였고, Mn 및 Cu 이온 치환된 시료에서는 증가하였다. CEMS 분석 결과 $Mn^{2+}$ 및 $Ni^{2+}$ 이온들은 주로 팔면체 자리를 치환하는 것으로 나타났으며, $Cu^{2+}$ 이온들은 팔면체, 사면체 자리를 모두 치환하는 것으로 나타났다. 부스펙트럼들의 세기비 $A_B/A_A$는 계산값과 측정값에 다소 차이가 있었으며, 이것은 M 치환이 A와 B자리의 Debye 온도에 영향을 주는 것으로 해석된다. B-자리 부스펙트럼의 비교적 큰 선폭값은 M 이온 치환에 기인한 B-자리의 M 이온분포가 초미세자기장에 미치는 분포효과로 나타났다.

• 한국분말재료학회지
• /
• 제9권6호
• /
• pp.381-393
• /
• 2002

Recent developments in nanocrystalline and nanocomposite rare earth-transition metal magnets are reviewed and emphasis is placed on research work at IFW Dresden. Principal synthesis methods include high energy ball milling, melt spinning, mold casting and hydrogen assisted methods such as reactive milling and hydrogenation-disproportionation-desorption-recombination. These techniques are applied to NdFeB-, PrFeB- and SmCo-type systems with the aim to produce high remanence magnets with high coercivity. Concepts of maximizing the energy density in nanostructured magnets by either inducing a texture via anisotropic HDDR or hot deformation or enhancing the remanence via magnetic exchange coupling are evaluated. With respect to high temperature applications melt spun $Sm(Co_{0.74}Fe_{0.1}Cu_{0.12}Zr_{0.04})_{7.5}$ ribbons were prepared, which showed coercivities of up to 0.53 T at 50$0^{\circ}C$. Partially amorphous $Nd_{60}Fe_xCo_{30-x}Al_{10}(0{\leq}x{\leq}30)$ alloys were prepared by copper mold casting. The effect of transition metal content on the glass-forming ability and the magnetic properties was investigated. The $Nd_{60}Co_{30}Al_{10}$ alloy exhibits an amorphous structure shown by the corresponding diffraction pattern. A small substitution of Co by 2.5 at.% Fe results In the formation of Fe-rich crystallites embedded in the Nd-rich amorphous matrix. The Fe-rich crystallites show hard magnetic behaviour at room temperature with a coercivity value of about 0.4 T, relatively low saturation magnetization and a Curie temperature of 500 K.

• Bulletin of the Korean Chemical Society
• /
• 제35권6호
• /
• pp.1749-1753
• /
• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.