• Title/Summary/Keyword: $CH_4/N_2$

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Copolymerization of Ethylene and Norbornene via Polymethylene Bridged Dinuclear Constrained Geometry Catalysts

  • Zhu, Yin-Bang;Jeong, Eung-Yeong;Lee, Bae-Wook;Kim, Bong-Shik;Noh, Seok-Kyun;Lyoo, Won-Seok;Lee, Dong-Ho;Kim, Yong-Man
    • Macromolecular Research
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    • v.15 no.5
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    • pp.430-436
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    • 2007
  • The dinuclear half-sandwich CGCs (constrained geometry catalyst) with a polymethylene bridge, $[Ti({\eta}^5 : {\eta}^1-indenyl)SiMe_2NCMe_3]_2(CH_2)_n]$[n = 6 (1) and 12 (2)], have been employed in the copolymerization of ethylene and norbornene (NBE). To compare the mononuclear metallocene catalysts; $Ti({\eta}^5 : {\eta}^1-2-hexylindenyl)SiMe_2NCMe_3$ (3), $(Cp^* SiMe_2NCMe_3)$Ti (Dow CGC) (4) and ansa-$Et(Ind)_2ZrCI_2$ (5), were also studied for the copolymerization of ethylene and NBE. It was found that the activity increased in the order: 1 < 2 < 3 < 5 < 4, indicating that the presence of the bridge between two the CGC units contributed to depressing the polymerization activity of the CGCs. This result strongly suggests that the implication of steric disturbance due to the presence of the bridge may playa significant role in slowing the activity. Dinuclear CGCs have been found to be very efficient for the incorporation of NBE onto the polyethylene backbone. The NBE contents in the copolymers formed ranged from 10 to 42%, depending on the polymerization conditions. Strong chemical shifts were observed at ${\delta}$42.0 and 47.8 of the isotactic alternating NBE sequences, NENEN, in the copolymers with high NBE contents. In addition, a resonance at 47.1 ppm for the sequences of the isolated NBE, EENEE, was observed in the $^{13}C-NMR$ spectra of the copolymers with low NBE contents. The absence of signals for isotactic dyad at 48.1 and 49.1 ppm illustrated there were no isotactic or microblock (NBE-NBE) sequences in the copolymers. This result indicated that the dinuclear CGCs were effective for making randomly distributed ethylene-NBE copolymers.

Estimation of Economics thorough Prediction of Methane Generation using IPCC Guideline from C Sanitary Landfill (IPCC가이드라인을 이용한 중소도시 C위생매립장의 메탄가스 발생량 예측을 통한 경제성 평가)

  • Lee, Sang-Woo;Park, Seo-Yun;Chang, In-Soo;Kang, Byung-Wook;Park, Sang-Chan;Yeon, Ik-Jun
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.189.1-189.1
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    • 2011
  • Global warming effect was intensified due to rapid growth of fossil fuel consumption caused by urbanization and industrialization. Various efforts was being done to solve the problems leading to anomaly climate such as flood, downpour, heavy snow. As a results of international efforts for management of global warming, Kyoto Protocol, which was passed in Kyoto, Japan in 1997, designated $CO_2$, $CH_4$, $N_2O$, HFCs, PFCs, $SF_6$ as a global warming gases. And IPCC(Intergovernmental Panel on Climate Change) suggested IPCC guideline for systematic establishment of national greenhouse gas inventory. Among five categories in IPCC guideline, the representative emission source of waste category is SWDS(solid waste disposal site). The concentrative research should progress for effective management of greenhouse gas related with waste. In this study, Tier1 and Tier2 methods which was suggested by 2006 IPCC(Intergovernmental Panel on Climate Change) guideline, was used to predict methane generation from C sanitary landfill located in Chungju area. To predict methane generation from C sanitary landfill, all factors were defaults values that were provided by 2006 IPCC guideline and Korea emission factors for Tier1 and Tier2 method. And economics of generated methane was estimated. From the predicted result using IPCC guideline, the methane generation was persistingly increased over a 9-year period(2000 ~ 2008). Aggregated amount of methane generation was about 3,017ton and 3,170ton predicted by Tier1 and Tier2, respectively. From the results of estimated economic value gained by generated methane from the C sanitary landfill for ten years from now(2010 ~ 2020), the profit was about 2.39 ~ 2.76 hundred million won.

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Properties of Zeolite Nanopowder Coated with Titanium Dioxide by Atomic Layer Deposition

  • Lee, Bo Kyung;Ok, Hae Ryul;Bae, Hye Jin;Kim, Hyug Jong;Choi, Byung Ho
    • Korean Journal of Materials Research
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    • v.26 no.3
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    • pp.149-153
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    • 2016
  • Nanosized zeolites were prepared in an autoclave using tetraethoxysilane (TEOS), tetrapropylammonium hydroxide (TPAOH), and $H_2O$, at various hydrothermal synthesis temperatures. Using transmission electron microscopy and particle size analysis, the nanopowder particulate sizes were revealed to be 10-300 nm. X-ray diffraction analysis confirmed that the synthesized nanopowder was silicalite-1 zeolite. Using atomic layer deposition, the fabricated zeolite nanopowder particles were coated with nanoscale $TiO_2$ films. The $TiO_2$ films were prepared at $300^{\circ}C$ by using $Ti[N(CH_3)_2]_4$ and $H_2O$ as precursor and reactant gas, respectively. In the TEM analysis, the growth rate was ${\sim}0.7{\AA}/cycle$. Zeta potential and sedimentation test results indicated that, owing to the electrostatic repulsion between $TiO_2$-coated layers on the surface of the zeolite nanoparticles, the dispersibility of the coated nanoparticles was higher than that of the uncoated nanoparticles. In addition, the effect of the coated nanoparticles on the photodecomposition was studied for the irradiation time of 240 min; the concentration of methylene blue was found to decrease to 48%.

Improvement of Radiosynthesis Yield of [11C]acetate ([11C]아세트산의 방사화학적 수율 증가를 위한 연구)

  • Park, Jun Young;Son, Jeongmin
    • The Korean Journal of Nuclear Medicine Technology
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    • v.22 no.2
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    • pp.74-78
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    • 2018
  • Purpose $[^{11}C]$acetate has been proved useful in detecting the myocardial oxygen metabolism and various malignancies including prostate cancer, hepatocellular carcinoma, renal cell carcinoma and brain tumors. The purpose of study was to improve the radiosynthesis yield of $[^{11}C]$acetate on a automated radiosynthesis module. Materials and Methods $[^{11}C]$acetate was prepared by carboxylation of grignard reagent, methylmagnesium chloride, with $[^{11}C]$$CO_2$ gas, followed by hydrolysis with 1 mM acetic acid and purification using solid phase extraction cartridges. The effect of the reaction temperature ($0^{\circ}C$, $10^{\circ}C$, $-55^{\circ}C$) and cyclotron beam time (10 min, 15 min, 20 min, 25 min) on the radiosynthesis yield were investigated in the $[^{11}C]$acetate labeling reaction. Results The maximum radiosynthesis yield was obtained at $-10^{\circ}C$ of reaction temperature. The radioactivities of $[^{11}C]$acetate acquired at $-10^{\circ}C$ reaction temperature was 2.4 times higher than those of $[^{11}C]$acetate acquired at $-55^{\circ}C$. Radiosynthesis yield of $[^{11}C]$acetate increased with increasing cyclotron beam time. Conclusion This study shows that radiosynthesis yield of $[^{11}C]$acetate highly dependent on reaction temperature. The best radiosynthesis yield was obtained in reaction of grignard reagent with $[^{11}C]$$CO_2$ at $-10^{\circ}C$. This radiolabeling conditions will be ideal for routine clinical application.

Partial Oxidation of Methane to $H_2$ Over Pd/Ti-SPK and Pd/Zr-SPK Catalysts and Characterization (Pd/Ti-SPK과 Pd/Zr-SPK 촉매상에서 수소 생산을 위한 메탄의 부분산화반응과 촉매의 특성화)

  • Seo, Ho-Joon;Kang, Ung-Il
    • Applied Chemistry for Engineering
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    • v.21 no.6
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    • pp.648-652
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    • 2010
  • Catalytic activities of the partial oxidation of methane (POM) to hydrogen were investigated over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK in a fixed bed flow reactor (FBFR) under atmosphere, and the catalysts were characterized by BET, XPS, XRD. The BET surface areas, pore volume and pore width of Horvath-Kawaze, micro pore area and volume of t-plot of Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were $284m^2/g$, $0.233cm^3/g$, 3.9 nm, $30m^2/g$, $0.015cm^3/g$ and $396m^2/g$, $0.324cm^3/g$, 3.7nm, $119m^2/g$, $0.055cm^3/g$, repectively. The nitrogen adsorption isotherms were type IV with hysteresis. XPS showed that Si 2p and O 1s core electronlevels of Ti-SPK and Zr-SPK substituted Ti and Zr shifted to slightly lower binding energies than SPK. The oxidation states of Pd on the surface of catalysts were $Pd^0$ and $Pd^{+2}$. XRD patterns showed that crystal structures of fresh catalyst changed amorphous into crystal phase after reaction. The conversion and selectivity of POM to hydrogen over Pd(5)/Ti-SPK and Pd(5)/Zr-SPK were 77, 84% and 78, 72%, respectively, at 973 K, $CH_4/O_2$ = 2, GHSV = $8.4{\times}10^4mL/g_{cat}{\cdot}h$ and were kept constant even after 3 days in stream. These results confirm superior activity, thermal stability, and physicochemical properties of catalyst in POM to hydrogen.

Estimation for the Variation of the Concentration of Greenhouse Gases with Modified Shannon Entropy (변형된 샤논 엔트로피식을 이용한 온실가스 농도변화량 예측)

  • Kim, Sang-Mok;Lee, Do-Haeng;Choi, Eol;Koh, Mi-Sol;Yang, Jae-Kyu
    • Journal of Environmental Science International
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    • v.22 no.11
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    • pp.1473-1479
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    • 2013
  • Entropy is a measure of disorder or uncertainty. This terminology is qualitatively used in the understanding of its correlation to pollution in the environmental area. In this research, three different entropies were defined and characterized in order to quantify the qualitative entropy previously used in the environmental science. We are dealing with newly defined distinct entropies $E_1$, $E_2$, and $E_3$ originated from Shannon entropy in the information theory, reflecting concentration of three major green house gases $CO_2$, $N_2O$ and $CH_4$ represented as the probability variables. First, $E_1$ is to evaluate the total amount of entropy from concentration difference of each green house gas with respect to three periods, due to industrial revolution, post-industrial revolution, and information revolution, respectively. Next, $E_2$ is to evaluate the entropy reflecting the increasing of the logarithm base along with the accumulated time unit. Lastly, $E_3$ is to evaluate the entropy with a fixed logarithm base by 2 depending on the time. Analytical results are as follows. $E_1$ shows the degree of prediction reliability with respect to variation of green house gases. As $E_1$ increased, the concentration variation becomes stabilized, so that it follows from linear correlation. $E_2$ is a valid indicator for the mutual comparison of those green house gases. Although $E_3$ locally varies within specific periods, it eventually follows a logarithmic curve like a similar pattern observed in thermodynamic entropy.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1625-1629
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    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Roles of Ki67 in Breast Cancer - Important for Management?

  • Yip, CH;Bhoo-Pathy, N;Daniel, JM;Foo, YC;Mohamed, AK;Abdullah, MM;Ng, YS;Yap, BK;Pathmanathan, R
    • Asian Pacific Journal of Cancer Prevention
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    • v.17 no.3
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    • pp.1077-1082
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    • 2016
  • Background: The three standard biomarkers used in breast cancer are the estrogen receptor (ER), progesterone receptor (PR) and human epidermal growth factor receptor 2 (HER2). The Ki-67 index, a proliferative marker, has been shown to be associated with a poorer outcome, and despite absence of standardization of pathological assessment, is widely used for therapy decision making. We aim to study the role of the Ki-67 index in a group of Asian women with breast cancer. Materials and Methods: A total of 450 women newly diagnosed with Stage 1 to 3 invasive breast cancer in a single centre from July 2013 to Dec 2014 were included in this study. Univariable and multivariable logistic regression was used to determine the association between Ki-67 (positive defined as 14% and above) and age, ethnicity, grade, mitotic index, ER, PR, HER2, lymph node status and size. All analyses were performed using SPSS Version 22. Results: In univariable analysis, Ki -67 index was associated with younger age, higher grade, ER and PR negativity, HER2 positivity, high mitotic index and positive lymph nodes. However on multivariable analysis only tumour size, grade, PR and HER2 remained significant. Out of 102 stage 1 patients who had ER positive/PR positive/HER2 negative tumours and non-grade 3, only 5 (4.9%) had a positive Ki-67 index and may have been offered chemotherapy. However, it is interesting to note that none of these patients received chemotherapy. Conclusions: Information on Ki67 would have potentially changed management in an insignificant proportion of patients with stage 1 breast cancer.

An Experimental Study of The J-T Cryocooler with Mixed Refrigerant (혼합 냉매를 이용한 극저온 J-T 냉동기 관한 실험적 연구)

  • 이경수;정상권
    • Progress in Superconductivity and Cryogenics
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    • v.3 no.1
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    • pp.64-68
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    • 2001
  • An experimental study on the Joule-Thomson cryocooler with the mixed refrigerant (MR) is described in this paper, J-T refrigeration experiment was performed with a single stage regular air-conditioning compressor The mixed refrigerant in the experiment was composed of 75% mol fraction of $N_2$. 30% moi fraction of CH$_4$. 30% moi fraction of $C_2$H$_{6}$. 10% mot fraction of $C_3$H$_{8}$ and 15% mot fraction of iso-C$_4$H$_{10}$. Oil mist in the MR stream could be eliminated completely by the glass microfiber filter. Since a single stage compressor that had been designed thor R22 is not appropriate for high Pressure ratio of the mixed refrigerant especially during the transient period. two modifications were incorporated to regular J-T refrigeration cycle. First. a Portion of the MR was by-passed at the inlet of the heat exchanger and transferred directly to 7he suction of the compressor in the modified system. Second, a buffer volume was Prepared to change the mass flow rate of refrigerant. The pressure ratio in J-T expansion device was relieved at the beginning of the operation due to the by-Pass scheme. but it gradually decreased during the transient Process as some of the MR component condensed at low temperature. The buffer volume at the suction side was used to increase the MR gas density in the system after the transient cool-down period. Form the experiment with the modified system, the refrigerator could reach the lowest temperature of -152$^{\circ}C$ without cooling load. and about -15$0^{\circ}C$ with 5 W of cooling load . . . .

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Climate Effects on Greenhouse Gas Emissions and Microbial Communities in Wetlands (기후변화가 습지 내 온실기체 발생과 미생물 군집구조에 미치는 영향)

  • Kim, Seon-Young;Kang, Ho-Jeong
    • Korean Journal of Agricultural and Forest Meteorology
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    • v.9 no.3
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    • pp.161-169
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    • 2007
  • Global climate changes including elevated $CO_2$, drought, and global warming may influence greenhouse gas emissions in wetlands. A variety of microbial communities including denitrifiers and methanogens play a key role in determining such processes. In this paper we summarize current knowledge on the effects of climate changes on $CO_2,\;CH_4$, and $N_2O$ production and microbial communities mediating those processes in wetlands. Elevated atmospheric $CO_2$ and warming generally increase gas emissions, but effects of droughts differ with gas type and drying level. The responses of microbial community to climate changes in terms of composition, diversity and abundance are still in question due to lack of studies in wetlands. Based on the present review, it is suggested that future studies on microbial processes should consider microbial community and relationships between microbial function and structure with diverse environmental factors including climate changes. Such knowledge would be crucial to better understand and predict accurately any shifts in ecological functions of wetlands.