• Applied Chemistry for Engineering
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• v.20 no.6
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• pp.603-611
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• 2009

Thermotropic liquid crystalline behavior of a homologous series of penta-O-4-{4'-(cyanophenylazo)phenoxy}alkyl-D-glucopyranoses(CAGETn, n = 2~10, the number of methylene units in the spacer) has been investigated. The CAGETn with n of 2 and 7 exhibited enantiotropic nematic phases whereas other derivatives showed monotropic nematic phases. This is the first report of glucose derivatives that form thermotropic nematic phases. The isotropic-nematic transition temperatures ($T_{iNS}$) of CAGETns and their entropy variation at $T_{iN}$ showed the odd-even effect as a function of n. This behavior was rationalized in terms of the change in the average shape of the side chains as the parity of the spacer is varied. This rationalization also accounts for the observed variation of nematic-crystalline phase transition temperatures ($T_{NkS}$) and associoated entropy change at $T_{Nk}$. The entropy change at $T_{iN}$ or $T_{Nk}$ reaches a mininum at n = 3, before it increases again for n = 4. This may be attributed to the difference in the arrangement of the side groups. The mesophase properties of CAGETns were entirely different from those reported for partially or fully alkylated glucopyranoses. This result suggests that the degree of substitution and chemical structure of the substituents play an important role in the formation of the mesophase structures in the liquid crystals.

• Journal of the Korean Magnetics Society
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• v.17 no.1
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• pp.14-17
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• 2007

Magnetic properties of transition metal doped $La_{0.5}Ca_{0.5}(Mn_{0.98}TM_{0.02})O_3$(TM=Cr and Ti) are studied. The samples are synthesized by the conventional solid-state method. Using vibrating sample magnetometer magnetization-temperature measurement were carried out with zero field cooling and field cooling at 50 Oe. Cr-doped sample shows cluster or spin glass like behavior while Ti doped does not. Curie temperature obtained were decreased from that of LCMO(245.5 K). Curie temperatures of Cr-doped and Ti-doped samples are 235.5 K and 232.7 K, respectively. The temperature-dependent coercivity $H_c(T)$ was also measured. The coercive force continuously decreases with the substitution of Cr and Ti, The result can be understood in terms of the interaction between defect and domain wall.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.443-454
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• 2013

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically $V^{5+}$, $Co^{2+}$, and $Ni^{2+}$-incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated.

• Applied Chemistry for Engineering
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• v.30 no.1
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• pp.81-87
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• 2019

In this study, synthetic methods and physical properties for a new class of glycidyl azide polymer (GAP) were investigated for energetic thermoplastic elastomers (ETPE). Four kinds of GAP copolymer polyols were synthesized by introducing nucleophiles such as azide, alkoxide and alkyl amine into poly(epichlorohydrin) (PECH). The GAP copolymer synthetic reaction can be evaluated as an environmental benign and efficient synthetic method due to the simultaneous one-step reaction using two kinds of nucleophiles and the complete consumption of sodium azide. The relative stoichiometric substitution ratio analysis and the progress of reaction were checked and monitored by inverse gated decoupled $^{13}C$ NMR and Fourier transform infrared (FT-IR) spectroscopy. The glass transition temperature and molecular weight were measured by differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. The synthesized poly($GA_{0.8}-butoxide_{0.2}$), poly($GA_{0.7}-n-butylamine_{0.3}$), poly($GA_{0.7}-dipropylamine_{0.3}$) and poly($GA_{0.7}-morpholine_{0.3}$) had a glass transition temperature ranged from -39 to $-26^{\circ}C$.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.20 no.4
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• pp.626-631
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• 2019

The policy-making and technological development for the supply expansion of eco-friendly automobiles has been continuing, but the internal combustion engines still accounts for about 95%. Also, in order to meet the stricter emission regulations of internal combustion engines based on fossil fuels, the proportion of after-treatments for vehicles and (ocean going) vessels is gradually increasing. This study is a basic study for the post-Euro-VI exhaust response of CNG buses, and it is to investigate the basic characteristics according to Pd substitution transition metal effect, catalyst volume effect and space velocity. A catalysts was prepared and tested using a model gas reactor. The NGOC catalyst with 3Pd exhibited the highest catalytic activity with 22% at $300^{\circ}C$, 48% at $350^{\circ}C$ and about 75% at $500^{\circ}C$. 3Co NGOC containing 3wt% of transition metal was excellent in oxidation ability, and it was small in size of 2nm, and the degree of catalyst dispersion was improved and de-NO/CO conversion was high. The volume of the NGOC-LNT-SCR catalyst system was optimal in the combination of 1.5+0.5+0.5 with a total score of 165, considering $de-CH_4/NOx$ performance and catalyst cost. For SV $14,000h^{-1}$, the $CH_4$ reduction performance was the highest at about 20%, while the SV $56,000h^{-1}$ was the lowest at about 5%. If the space velocity is small, the flow velocity decreases and the time remaining in the catalyst volume become long, so that the harmful gas was reduced.

• Iberoamérica
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• v.13 no.1
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• pp.123-152
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• 2011

The long standing people's culture of Latin America based on social solidarity of the communities makes the political relations between the leader and the people very different from them of the european societies based on the representative democracy. At any rate, the main stream of the Populist Discourses sees the real populist political processes with the pejorative senses attributing the demagogue style of the leaders. In these sense, it is very important to re-consider the populism discourses of Ernesto Laclau who thinks that the populism is a way of interpreting the emergence of the people to establish the social demands in the context of populist real politics. According to Laclau, "the populism seeks for the radical reconfiguration of the revolt of the 'Status Quo' and new order". This work will confirm if this interpretation of Laclau can be applied to Peronist political regime. Meanwhile the first group of the orthodox line of the discourses on populism including Gino Germani shows that the populism is a political movement based on the manipulation and demagogue by the charismatic leader of the irrational mass during the period in transition after the crises of the traditional oligarchy in Latin America. And another line of the main stream of discourses on populism including Cardoso and O'Donnell says that the populism is a political phenomena in a period of transition towards the modernization and the national development by means of the industrialization through the substitution of the imports and the alliance between the classes after the 1930's. But these principal interpretations on populism disregards that in Argentina many urban poor working class people had lived under the racist, unequal painful social relations due to the underestimation and the discrimination by the upper and the middle class with many intellectuals. But Peronism had considered them as the new social subjects with human dignities. And so we have to rethink the clientelism also with another meanings. In this sense, the theories of Ernesto Laclau on populism is very helpful to illuminate the sensitive and ambiguous meanings of Peronism. Especially Peronism makes the urban working class maintain their life styles more tended to them of the traditional communities and go towards the anti-Status Quo. That is a key of success of Peronism not only that time but until these days. And so this study will show that it is the most important thing that Peronist regime had made the emergence of the 'people' in the meaning of advancing the democracy in Argentina.

• Proceedings of the Materials Research Society of Korea Conference
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• 1994.11a
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• pp.1-1
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• 1994

;The electronic state calculations for various types of ceramic materials have beell performed by the use of $DV-X\;{\alpha}$ cluster method. The molecular orbital levels and wave functions for model clusters have been computed to study the electronic properties ami chemical bonding of the ceramics. For ${\beta}-sialon(Si_{6-z}Al_zO_zN_{8-z})$ which is a high temperature structural material based on ${\beta}-Si_3N_4$, we have made model cluster calculations to estimate the strength of chemical bonding between atoms by the Mulliken population analysis. It is found that the covalent bonding between Si and N atoms is very strong in pure ${\beta}-Si_3N_4$, but the covalency around solute atom is considerably weakened when Si atom is substituted by AI. This tendency is enhanced by an additional substitution of oxygen atom for N. The result calculated can well explain the experimental data of changes in mechanical properties such as the reductions of Young's modulus and Vickers hardness with increment of z-value in ${\beta}-sialon$. Various model clusters for transition metal oxides which show many interesting physical and chemical properties have also been calculated. High-valent perovskite-type iron oxides EMFe0_3E(M=Ca and Sr) possess very interesting magnetic and chemical properties. In these oxides, iron exists as $Fe^{4+}$ state, but the experimental measurement of Mossba~er effect suggests that disproportionation $2Fe^{4+}=Fe^{3+}+Fe^{5+}$ takes place for $CaFe0_3$ at low temperatures. The model cluster calculations for these compounds indicated the existence of considerably strong covalent bonding of Fe-O. The calculations of hyperfine interaction at iron neucleus show very good agreement with the experimental Mossbauer measurements. The result calculated also implies that the disproportionation reaction is strongly possible by assuming the quenching of breathing phonon mode at low temperatures.tures.

• Journal of the Korean Chemical Society
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• v.31 no.4
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• pp.352-358
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• 1987

Rate constants for the hydrolysis of para-substituted phenyl N-(p-chlorobenzoyl)chloroformimidate (I) derivatives in 1 : 4 dioxane-water at $25^{\circ}C$ have been determined. Rate data, substituent effect $(\rho\>{\rho}^+)$, product analysis and MO calculation indicate that the uncatalyzed reaction proceeds through an $S_N1$ mechanism involving the formation of azocarbonium ion (II) below pH 3.0, and the base-catalyzed reaction proceeds through an $S_N2$ mechanism via transition state (III) above pH 4.0. The relative stability of four peri planar conformational isomers were (E-ap) > (Z-ap) > (E-sp) > (Z-ap), respectively, and the most stable stereo structures shows that the Y-substituted phenyl group $(C_6H_4-Y)$ occupy vertical $(90^{\circ})$ position on the plane of the benzimidochloroformyl group in (E-ap) conformer. The nucleophilic substitution of water molecule occurs by sigma attack to the activatived azomethine carbon atom of (I) derivatives.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.2955-2959
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• 2011

Second-order rate constants for nucleophilic substitution reactions of 2,4-dinitrophenyl benzenesulfonate 1a with a series of alicyclic secondary amines in MeCN have been measured spectrophotometrically and compared with those reported previously for the corresponding reactions performed in aqueous medium to investigate the effect of medium on reactivity and reaction mechanism. The amines employed in this study are found to be more reactive in the aprotic solvent than in $H_2O$. The reactions of 1a in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.58, which contrasts to the curved Br${\o}$nsted-type plot reported previously for the corresponding reactions performed in the aqueous medium (i.e., ${\beta}_2$ = 0.86 and ${\beta}_1$ = 0.38). Accordingly, it has been concluded that the reaction mechanism changes from a stepwise mechanism to a concerted pathway upon changing the medium from $H_2O$ to MeCN. Reactions of Y-substituted phenyl benzenesulfonates 1a-c with piperidine in MeCN result in a linear Br${\o}$nsted-type plot with ${\beta}_{lg}$ = -1.31, indicating that expulsion of the leaving group is significantly more advanced than bond formation in the transition state. The trigonal bipyramidal intermediate ($TBPy^{\pm}$) proposed previously for the reactions in $H_2O$ would be highly unstable in MeCN due to strong repulsion between the negative charge in $TBPy^{\pm}$ and the negative dipole end of MeCN. Thus, destabilization of $TBPy^{\pm}$ in MeCN has been concluded to change the reaction mechanism from a stepwise mechanism to a concerted pathway.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3947-3951
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• 2011

The nucleophilic substitution reactions of Y-aryl ethyl chlorothiophosphates with X-pyridines are studied kinetically in acetonitrile at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Me. The substituents of X = 4-CN and 4-Ac show great positive deviations from both the Hammett and Bronsted plots. The Hammett plots for substituent Y variations in the substrates exhibit biphasic concave upwards with a minimum point at Y = H. The obtained values of the cross-interaction constants (${\rho}_{XY}$) are all in spite of the biphasic free energy correlations for both substituent X and Y variations, since the ${\rho}_X$values with both the strongly and weakly basic pyridines are almost constant. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed where the distance between X and Y does not vary from the intermediate to the second transition state. A frontside attack is proposed with the strongly basic pyridines based on the considerably great magnitudes of ${\rho}_X$ and ${\beta}_X$ values and a backside attack is proposed with the weakly basic pyridines based on the relatively small magnitudes of ${\rho}_X$ and ${\beta}_X$. The positive deviations of the two strong ${\pi}$-acceptor parasubstituents, X = 4-Ac and 4-CN, from both the Hammett and Bronsted plots are rationalized by the great extents of bond formation and breaking.