• Title/Summary/Keyword: Substitution reaction

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Synthesis, Characterizations, and Applications of Metal-Ions Incorporated High Quality MCM-41 Catalysts (고품질 금속 이온 첨가 MCM-41 분자체 촉매의 제법, 특성화 및 응용 반응)

  • Lim, Steven S.;Haller, Gary L.
    • 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.

Preparation of Azidated Polybutadiene(Az-PBD)/Ethylene-Vinyl Acetate Copolymer(EVA) Blends for the Application of Energetic Thermoplastic Elastomer (에너지함유 열가소성탄성체 적용을 위한 아지드화 폴리부타디엔/에틸렌-비닐아세테이트 공중합체 블렌드 제조)

  • Yoon, Sang Won;Choi, Myung Chan;Chang, Young-Wook;Noh, Si-Tae;Kwon, Soon Kil
    • Korean Chemical Engineering Research
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    • v.53 no.3
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    • pp.282-288
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    • 2015
  • A new energetic thermoplastic elastomer based on the azidated polybutadiene(Az-PBD)/ethylene vinyl acetate copolymer (EVA) blends was prepared, and structure and properties of the blends were invetigated by SEM, DSC, DMA, tensile testing and combustion test. The Az-PBD was synthesized via a two-step process involving the addition reaction of commercially available 1,2-PBD with $Br_2$ and subsequent nucleophilic substitution reaction of the brominated PBD with $NaN_3$. EVA/Az-PBD with 90/10, 80/20, 70/30 (wt/wt) was prepared by a solution blending. SEM, DSC, and DMA results revealed that the blends are partially compatible and Az-PBD is dispersed in continuous EVA matrix. Tensile test showed that modulus and tension set increased while elongation-at-break of the blends decreased with increasing Az-PBD content in the blends, but all the blends showed a elongation at break as high as 700% and a tension set of less than 5%, indicating that the blends are typically elastomeric. Combustion test showed that, with increasing Az-PBD content in the blend, higher energy can be released.

Photochromic Properties of Cellulose Derivatives Having Spirobenzopyran Group (스피로벤조피란을 포함하는 셀룰로오스 유도체의 광변색 특성)

  • Xiangdan, Li;Kim, Eun-Kyoung;Lee, Myong-Hoon
    • Polymer(Korea)
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    • v.29 no.1
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    • pp.25-31
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    • 2005
  • Cellulose acetate derivatives containing 6-(p-hexyloxyphenyl)carbonyl spirobenzopyran (CA-COSP) were prepared from base-catalyzed etherification of cellulose acetate, and their physical and photochromic properties were characterized. The degree of substitution of COSP was calculated from the amount of residual hydroxyl groups in cellulose acetate measured by the $^1H$-NMR and UV spectrometric data. It was ranging from 0.87 to 45.5% depending on the reaction condition. UV/vis spectrometry of the resulting CA-COSP revealed that the polymer shows a reversible color change by changing its color from colorless to blue upon UV irradiation forming a merocyanine structure, and returning back again to colorless spiropyran structure by visible light or by heat. The rate of color change was faster in solution than in the film. In the more polar solvent, the more stable was the resulting merocyanine, and the slower was the rate of reverse reaction to spiropyran. Compared to COSP blended with cellulose acetate, in which a phase separation was observed for samples containing more than 0.9 wt% of COSP, up to 48 wt% of COSP could be blended in CA-COSP without phase separation.

Analysis and Verification of Ancient DNA (고대 DNA의 분석과 검증)

  • Jee, Sang-hyun;Seo, Min-seok
    • Korean Journal of Heritage: History & Science
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    • v.40
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    • pp.387-411
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    • 2007
  • The analysis of ancient DNA (aDNA) has become increasingly considerable anthropological, archaeological, biological and public interest. Although this approach is complicated by the natural damage and exogenous contamination of a DNA, archaeologists and biologists have attempted to understand issues such as human evolutionary history, migration and social organization, funeral custom and disease, and even evolutionary phylogeny of extinct animals. Polymerase chain reaction(PCR) is powerful technique that analyzes DNA sequences from a little extract of an ancient specimen. However, deamination and fragmentation are common molecular damages of aDNA and cause enzymatic inhibition in PCR for DNA amplification. Besides, the deamination of a cytosine residue yielded an uracil residue in the ancient template, and results in the misincorporation of an adenine residue in PCR. This promotes a consistent substitution (cytosine thymine, guanine adenine) to original nucleotide sequences. Contamination with exogenous DNA is a major problem in aDNA analysis, and causes oversight as erroneous conclusion. This report represents serious problems that DNA modification and contamination are the main issues in result validation of aDNA analysis. Now, we introduce several criterions suggested to authenticate reliance of aDNA analysis by many researchers in this field.

Preparation and Characterization of a Cross-Linked Anion-Exchange Membrane Based on PVC for Electrochemical Capacitor (전기화학 캐퍼시터용 PVC기반 가교 음이온교환 멤브레인의 제조 및 특성)

  • Kim, Young-Ji;Kim, Soo-Yeoun;Choi, Seong-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.38 no.3
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    • pp.903-913
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    • 2021
  • Three-type PVC membranes denoted by AEM-1, AEM-2, and AEM-3 with a cross-linked anion-exchange group were prepared by substitution reaction of PVC with triethyldiamine (TEDA), 1,4-dimethylpiperazine (DMP), and 1,4-bis(imidazol-1-ylmethyl)benzene (BIB) in cyclohexanone, respectively. We confirmed the successful preparation of the AEM-1, AEM-2, and AEM-3 via ionic conductivity (S/cm), water uptake (%), contact angle, ion-exchange capacity (meq/g), thermal properties, SEM and XPS analysis, respectively. The electrochemical capacitor experiments using PVC membrane with cross-linked anion-exchange group in organic electrolytes were performed. The prepared AEM-1, AEM-2 AEM-3 have a good stability by charge and discharge performance in organic electrolyte. As a result, the AEM-2 and AEM-3 membrane based on PVC prepared by the solvent casting method after substituent reaction is suitable for the use as a separator in organic electrochemical capacitor (supercapacitor).

Electrochemical Characteristics of LiNi0.5Mn1.5O4 Spinel as 5 V Class Cathode Material for Lithium Secondary Batteries (5V급 고전압 양극 LiNi0.5Mn1.5O4 Spinel의 제조와 전기화학적 특성에 관한 연구)

  • Jeon, Sang-Hoon;Oh, Si-Hyoung;Lee, Byung-Jo;Cho, Won-Il;Cho, Byung-Won
    • Journal of the Korean Electrochemical Society
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    • v.8 no.4
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    • pp.172-176
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    • 2005
  • Recently, many researches on the high-voltage 5 V class cathode material have focused on $LiNi_{0.5}Mn_{1.5}O_4$, where $Mn^{3+}$ in the existing $LiMn_2O_4 (Li[Mn^{3+}][Mn^{4+}]O_4)$ is replaced by $Ni^{2+}(Li[Ni^{2+}]_{0.5}[Mn^{4+}]_{1.5}O_4)$ in order to utilize $Ni^{2+}/Ni^{4+}$ redox reaction in the 5V region. The partial substitution of Mn in $LiMn_2O_4$ for other transition metal element, $LiM_yMn_{1-y}O_4$(M=Cr, Al, Ni, Fe, Co, Cu, Ga etc) is known as a good solution to overcome the problems associated with $LiMn_2O_4$ like the gradual capacity fading. In this study, we synthesized $LiNi_{0.5}Mn_{1.5}O_4$ through a mechanochemical process and investigated its morphological, crystallographic and electrochemical characteristics. The results showed that 4 V peaks had been found in the cyclic volammograms of the synthesized powders due to the existence of $Mn^{3+}$ from the incomplete substitution of $Ni^{2+}$ for $Mn^{3+}$ implying that the mechanochemical activation alone was not good enough to synthesize an exact stoichiometric compound of $LiNi_{0.5}Mn_{1.5}O_4$. The synthetic condition of mechanochemical process, such as type of starting materials, ball-mill and calcination condition was optimized for the best electrochemical performance.

Crystallization and Magnetic Properties of Iron Doped La-Ba-Mn-O (Fe이 치환된 LaBaMnO계 산화물의 중성자 회절 및 Messbauer분광학연구)

  • Choi, Kang-Ryong;Kim, Sam-Jin;Shim, In-Bo;Kim, Chul-Sung
    • Journal of the Korean Magnetics Society
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    • v.14 no.1
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    • pp.38-44
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    • 2004
  • The iron doped colossal magnetoresistance materials with La-Ba-Mn-O perovskites structure have been synthesized by chemical reaction of sol-gel methods. Their crystallographic and magnetic properties have been studied with x-ray diffraction, VSM, RBS, Mossbauer spectroscopy, and magnetoresistance measurements. The crystal structure of the La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$ at room temperature was determined to be orthorhombic of Pnma. The lattice parameters a$\_$0/ and c$\_$0/ increased gradually, but b$\_$0/ deceased with increase of iron substitution. The magnetization and coercivity deceased, also the Curie temperature decreased from 360 K as x increased from 0.00 to 0.05. Magnetoresistence measurements were carried out, and the maximum MR ($\Delta$$\rho$/$\rho$(0)) was observed at 281 K, about 9.5 % in 10 kOe. The temperature of maximum resistance (R$\_$MAX/) decreased with increasing substitution of Fe ions and a semiconductor-metal transition temperature (T$\_$SC-M/) decreased too. This phenomena show that ferromagnetic transition temperature decreased by substituting Fe for Mn ions, it decreases double exchange interaction. This result accords with magnetic structure of neutron diffraction. Mossbauer spectra of La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$were taken at various temperatures ranging from 15 to 350 K. With lowering temperature of the sample, two magnetic phases were increased and finally it showed the two sharp sextets of spectra at 15 K. The isomer shift at all temperature range is about 0.3 mm/s relative to Fe metal, which means that both Fe ions are Fe$\^$3+/ states.Fe$\^$3+/ states.

Determination of metabolites of prostanozol in human urine by LC/ESI/MS and GC/TOF-MS (LC/ESI/MS와 GC/TOF-MS를 이용한 인체뇨시료에서의 Prostanozol 대사체 검출)

  • Yum, Tae-Woo;Paeng, Ki-Jung;Kim, Yun-Je
    • Analytical Science and Technology
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    • v.24 no.3
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    • pp.173-182
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    • 2011
  • This research examined prostanozol and its metabolites in urine of women who took the medicine (prostanozol). Prostanozol and its metabolites were successfully separated and detected by using LC/ESI/MS and GC/TOF-MS. Mass spectrum of LC/ESI/MS estimated molecular weight of Prostanozol and its metabolites and that of GC/TOF-MS verified them. For M1, carbon number 17 of Prostanozol substituted to a keto group and it is called 17-keto-Prostanozol. M2 turned out to be hydroxy-17-keto-Prostanozol. It came from substitution of one hydroxyl group of pyrazole nucleus and A-ring of M1. Substitution of one hydroxyl group of B-ring or C-ring became M3, hydroxy-17-keto-Prostanozol. M4 was found to be a hydroxy-17-keto-Prostsnozol transposed from one hydroxyl group to a D-ring. M5 has a hydroxyl group of carbon number 17. One hydroxyl group is substituted from B-ring or C-ring and it is assumed to be hydroxy-17-hydroxy-Prostanozol. M6 was turned out to be dihydroxy-17-keto-Prostanozol transposed from one hydroxyl group to pyrazole nucleus or A-ring and to B-ring or C-ring. Like M6, M7 has a keto group at carbon number 17 and was identified as dihydroxy-17-keto-Prostanozol. M7 has one hydroxyl group at pyrazole nucleus or A-ring and also at D-ring. At last M8 was found to be dihydroxy-17-hydroxy-Prostanozol. Pyrazole nucleus or A-ring has got one hydroxyl group and other rings were substituted to another hydroxyl group. From above, M5, M7 and M8 were verified as new metabolites that were not discovered yet. Prostanozol and all of the 8 metabolites formed glucuronic conjugates as a result of conjugation reaction test in human body. Some of 8 metabolites were excreted without forming conjugates. Particularly M6 and M7 were excreted as sulfate conjugates.

THE EFFECT OF SURFACE TREATMENT OF THE CERVICAL AREA OF IMPLANT ON BONE REGENERATION IN MINI-PIG (미니돼지에서 발치 후 즉시 임플란트 매식시 치경부 표면처리가 골재생에 미치는 효과)

  • Cho, Jin-Yong;Kim, Young-Jun;Yu, Min-Gi;Kook, Min-Suk;Oh, Hee-Kyun;Park, Hong-Ju
    • Journal of the Korean Association of Oral and Maxillofacial Surgeons
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    • v.34 no.3
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    • pp.285-292
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    • 2008
  • Purpose: The present study was performed to evaluate the effect of surface treatment of the cervical area of implant on bone regeneration in fresh extraction socket following implant installation. Materials and methods: The four minipigs, 18 months old and 30 kg weighted, were used. Four premolars of the left side of both the mandible and maxilla were extracted. ${\phi}$3.3 mm and 11.5 mm long US II plus implants (Osstem Implant co., Korea) with resorbable blasting media (RBM) treated surface and US II implants (Osstem Implant co., Korea) with machined surface at the top and RBM surface at lower portion were installed in the socket. Stability of the implant was measured with $Osstell^{TM}$ (Model 6 Resonance Frequency Analyser: Integration Diagnostics Ltd., Sweden). After 2 months of healing, the procedures and measurement of implant stability were repeated in the right side by same method of left side. At four months after first experiment, the animals were sacrificed after measurement of stability of all implants, and biopsies were obtained. Results: Well healed soft tissue and no mobility of the implants were observed in both groups. Histologically satisfactory osseointegration of implants was observed with RBM surface, and no foreign body reaction as well as inflammatory infiltration around implant were found. Furthermore, substantial bone formation and high degree of osseointegration were exhibited at the marginal defects around the cervical area of US II plus implants. However, healing of US II implants was characterized by the incomplete bone substitution and the presence of the connective tissue zone between the implant and newly formed bone. The distance between the implant platform (P) and the most coronal level of bone-to-implant contact (B) after 2 months of healing was $2.66{\pm}0.11$ mm at US II implants group and $1.80{\pm}0.13$mm at US II plus implant group. The P-B distance after 4 months of healing was $2.29{\pm}0.13$mm at US II implants group and $1.25{\pm}0.10$mm at US II plus implants group. The difference between both groups regarding the length of P-B distance was statistically significant(p<0.05). Concerning the resonance frequency analysis (RFA) value, the stability of US II plus implants group showed relatively higher RFA value than US II implants group. Conclusion: The current results suggest that implants with rough surface at the cervical area have an advantage in process of bone regeneration on defect around implant placed in a fresh extraction socket.

Mutation Analysis of Korean Patients with Glycogen Storage Disease Type Ia (한국인 당원병 제 Ia형 환자의 돌연변이 분석)

  • Kim, Jong-Won;Park, Ji-Yeon;Seo, Jeong-Kee
    • Pediatric Gastroenterology, Hepatology & Nutrition
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    • v.4 no.2
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    • pp.213-217
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    • 2001
  • Purpose: Glycogen storage disease type Ia (GSD Ia) is an autosomal recessive disorder of glycogen metabolism caused by glucose-6-phosphatase (G6Pase) deficiency. The clinical manifestations of G6Pase deficiency include growth retardation, hepatomegaly, hypoglycemia, lactic acidemia, hyperlipidemia and hyperuricemia. Many mutations of this gene have been found worldwide in various ethnic groups, establishing the molecular basis of GSD Ia. To elucidate a spectrum of the G6Pase gene mutations in Korean, we analyzed mutations in Korean patients with GSD Ia. Methods: Both alleles of 9 unrelated GSD 1a patients were studied by PCR and direct DNA sequencing methods. In all patients, GSD 1a was diagnosed by the enzyme assay for the liver biopsy specimen. Results: In Korean, the most prevalent mutation was g727t substitution in exon 5, which has been reported to cause abnormal mRNA splicing: Sixteen out of 18 alleles were found to have this mutation. In addition, we identified one novel mutation, a c611g, converting a proline to an alanine at codon 178. Conclusion: Our findings suggest that a screening for the g727t mutation by noninvasive molecular method can detect most cases of GSD Ia in Korean patients.

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