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.
Effects of temperature and additives on the stability of actomyosin extracted from skeletal muscle of Israeli carp, Cyprinus carpio nudus, were studied by analyzing free SH-group, ATP-sensitivity and Ca-ATPase activity. The used additives were sucrose, sorbitol, Na-glutamate and L-cysteine. Furthermore, the denaturation constant($K_D$), protective effect(${\Delta}E/M$) and the other thermo-dynamic parameters on protein denaturation are systematically discussed. The actomyosin showed $4.12{\sim}4.68 mg/ml$ in protein concentration, $2.63{\sim}2.93\%$ in ribonucleic acid to the protein, $1:2.20{\sim}2.63$ in the binding ratio of myosin and actin, $4.33{\sim}5.26\%$ in fat content, 109.78 in ATP-sonsitivity, $0.159{\sim}0.201\;{\mu}M-Pi/min/mg-protein$ in Ca-ATPase activity and $3.3{\sim}3.4M/10^5$g-protein in free SH-group content. The first-order rate plots were obtained on the decrease of Ca-ATPase activity and ATP-sensitivity with an increase in temperature, while the free SH-group was increased to $60^{\circ}C$ and decreased rapidly above the temperature. The half-life of Ca-ATPase activity on the actomyosin Ca-ATPase was 280 min at $12^{\circ}C$, 125 min at $20^{\circ}C$, 55 min at $30^{\circ}C$ and 13 min at $40^{\circ}C$, and activation energy, activation enthalpy, activation entropy and free energy of the proteins at $20^{\circ}C$ wene 5,395 cal/mole, 4,814 cal/mole, -40.42 e.u. and 17,626 cal/mole, respectively. The protective effect of the additives on the actomyosin Ca-ATPase showed that the most effective material is $3\%$ sorbitol and followed in the order of $8\%$ Na-glutamate, $1\%$ sucrose and $1\%$ L-cysteine. The actomyosin was more stable at $-30^{\circ}C$ than at $0^{\circ}C$ and $-20^{\circ}C$. and when the additives were used in the low temperature storage, $8\%$ Na-glutamate was the most effective. $3\%$ sorbitol, $1\%$ sucrose and $1\%$ L-cysteine was to become lower in the order.
Compounds of $Y_{3-x}Ce_{x}Fe{5}O_{12}$(x=0.0, 0.1, 0.2, and 0.3) were prepared using the sol-gel method. The XRD measurements show that these samples have only a single phase of the garnet structure regardless of the amount of Ce substitution. The lattice constants of x = 0.0 and x = 0.3 were found to be a$_0$ = 12.3758 ${\pm}$0.0005 ${\AA}$ and 12.4062 ${\pm}$0.0005 ${\AA}$, respectively. The lattice constant increases linearly with increasing Ce concentration. The saturation magnetization was not changed flirty, with increasing Ce concentration, but coercivity decreased form 18.3 Oe to 5.8 Oe as x increased form x = 0.0 to x = 0.1. Mossbauer spectra of $Y_{3-x}Ce_{x}Fe{5}O_{12}$ were measured at various absorber temperatures from 13 K to Neel temperature. The Mossbauer spectra were fitted by least-squares technique with two subpatterns of Fe sites in the structure and corresponding to the 16a and 24d site. The temperature dependence of the magnetic hyperfine field in $^{57}$/Fe nuclei at the tetrahedral 240 and octahedral 16a sites were analyzed based on the Neel theory of ferrirnagnetism. The result of the Debye temperatures indicated that the inter-atomic binding force for the 24d site was larger than that for the 16a site.
Journal of the Korean Crystal Growth and Crystal Technology
/
v.10
no.3
/
pp.189-198
/
2000
The stochiometric mixture of evaporating materials for the $CuGaSe_2$single crystal thin films were prepared from horizontal furnace. Using extrapolation method of X-ray diffraction patterns for the polycrystal $CuGaSe_2$, it was found tetragonal structure whose lattice constant $a_0}$ and $c_0$ were 5.615 $\AA$ and 11.025 $\AA$, respectively. To obtains the single crystal thin films, $CuGaSe_2$mixed crystal was deposited on throughly etched GaAs(100) by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $610^{\circ}C$ and $450^{\circ}C$ respectively, and the growth rate of the single crystal thin films was about 0.5$\mu\textrm{m}$/h. The crystalline structure of single crystal thin films was investigated by the double crystal X-ray diffraction (DCXD). Hall effect on this sample was measured by the method of van der Pauw and studied on carrier density and mobility depending on temperature. From Hall data, the mobility was likely to be decreased by pizoelectric scattering in the temperature range 30 K to 150 K and by polar optical scattering in the temperature range 150 K to 293 K. The optical energy gaps were found to be 1.68 eV for CuGaSe$_2$sing1e crystal thin films at room temperature. The temperature dependence of the photocurrent peak energy is well explained by the Varshni equation then the constants in the Varshni equation are given by $\alpha$ = $9.615{\times}10^{-4}$eV/K, and $\beta$ = 335 K. From the photocurrent spectra by illumination of polarized light of the $CuGaSe_2$single crystal thin films. We have found that values of spin orbit coupling $\Delta$So and crystal field splitting $\Delta$Cr was 0.0900 eV and 0.2498 eV, respectively. From the PL spectra at 20 K, the peaks corresponding to free bound excitons and D-A pair and a broad emission band due to SA is identified. The binding energy of the free excitons are determined to be 0.0626 eV and the dissipation energy of the acceptor-bound exciton and donor-bound exciton to be 0.0352 eV, 0.0932 eV, respectively.
Jung, Jong Hwa;Cho, Sung Bae;Kim, Jineun;Kim, Jae Sang;Lee, Shim Sung
Analytical Science and Technology
/
v.6
no.1
/
pp.29-37
/
1993
Some new podands containing phenyl(B), benzyl(Bz), pyridine(Py), quinoline(Q) and naphthalene(Np) as end-groups, and oxygen(O) and sulfur(S) in ether chains as donor atoms have been synthesized. The univalent cation binding characteristics of these podands have been studied by NMR titration and solvent extraction. By NMR titration we have found that the most of podands form 1:1 complexes with $Ag^+$ ion. Especially, the substituted sulfur atoms in ether chains show the effects to enhance the stabilities. We also carried out the extractions of univalent cation picrates including alkaline metal, $Ag^+$, $Tl^+$ and $NH_4{^-}$ ions from aqueous to chloroform layer by using these podands. We found that the extractabilities of $Ag^+$ ion with the quinoline-containing podands such as, $Q_2O_4$, $Q_2O_5$ and $BQO_5$ were 86.8, 86.6 and 48.0% respectively, but the naphthalene-containing podands such as, $Np_2O_4$ and $Np_2O_5$ extracted quite small amount. Otherwise, in cases of $Bz_2O_3S_2$(89.4%), $B_2O_2S_2$(96.8%), $B_2O_3S_2$(58.9%), $Py_2O_2S_2$(58.8%), $Py_2O_3S_2$(42.1%), and $B_2O_4S$(15.0%), interestingly, $Bz_2O_3S_2$ which have sulfur atoms and benzyl groups showed the highest extraction selectivity for $Ag^+$ ion. This result seems due to not only the strong interaction of $Ag^+$ ion with sulfur donors according to the HSAB theory, but also the effective ${\pi}-{\pi}$ stacking interaction between two aromatic end-groups which is enhanced by the flexible methylene spacing group in benzyl groups instead of phenyl groups. The extraction coefficients gave the similar tendency as the extractabilities and the stabilities. From these results, it could be concluded that the predominant factor affected to extraction coefficients is the stabilities, which are strongly influenced by the structures of podands.
Ki-Kyung Chjo;Yong-Kook Choi;Sang-Bock Kim;Jong-Ki Park;Dong-Hwa Park
Journal of the Korean Chemical Society
/
v.36
no.6
/
pp.894-905
/
1992
Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$$10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$$10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$$10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.
Journal of the Korean Crystal Growth and Crystal Technology
/
v.10
no.6
/
pp.425-433
/
2000
The stochiometric mix of evaporating materials for the $CuGaTe_2$single crystal thin films was prepared from horizontal furnance. Using extrapolation method of X-ray diffraction patterns for the $CuGaTe_2$polycrystal, it was found tetragonal structure whose lattice constant $a_0 and c_0$ were 6.025 $\AA$ and 11.931 $\AA$, respectively. To obtain the single crystal thin films, $CuGaTe_2$mixed crystal was deposited on throughly etched semi-insulator GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $670^{\circ}C$ and $410^{\circ}C$ respectively, and the thickness of the single crystal thin films is 2.1$\mu\textrm{m}$. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). Hall effect on this sample was measured by the method of van der Pauw and studied on carrier density and mobility dependence on temperature. The carrier density and mobility of $CuGaTe_2$single crystal thin films deduced from Hall data are $8.72{\times}10{23}$개 $\textrm m^3$, $3.42{\times}10^{-2}$$\textrm m^2$/V.s at 293K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the $CuGaTe_2$single crystal thin film, we have found that the values of spin orbit coupling $\Delta$s.o and the crystal field splitting $\Delta$cr were 0.0791 eV and 0.2463 eV at 10 K, respectively. From the PL spectra at 10 K, the peaks corresponding to free bound excitons and D-A pair and a broad emission band due to SA is identified. The binding energy of the free excitons are determined to be 0.0470 eV and the dissipation energy of the donor-bound exciton and acceptor-bound exciton to be 0.0490 eV, 0.0558 eV, respectively.
Purpose: Neuroreceptor PET studies require 60-120 minutes to complete and head motion of the subject during the PET scan increases the uncertainty in measured activity. In this study, we investigated the effects of the data-driven head mutton correction on the evaluation of endogenous dopamine release (DAR) in the striatum during the motor task which might have caused significant head motion artifact. Materials and Methods: $[^{11}C]raclopride$ PET scans on 4 normal volunteers acquired with bolus plus constant infusion protocol were retrospectively analyzed. Following the 50 min resting period, the participants played a video game with a monetary reward for 40 min. Dynamic frames acquired during the equilibrium condition (pre-task: 30-50 min, task: 70-90 min, post-task: 110-120 min) were realigned to the first frame in pre-task condition. Intra-condition registrations between the frames were performed, and average image for each condition was created and registered to the pre-task image (inter-condition registration). Pre-task PET image was then co-registered to own MRI of each participant and transformation parameters were reapplied to the others. Volumes of interest (VOI) for dorsal putamen (PU) and caudate (CA), ventral striatum (VS), and cerebellum were defined on the MRI. Binding potential (BP) was measured and DAR was calculated as the percent change of BP during and after the task. SPM analyses on the BP parametric images were also performed to explore the regional difference in the effects of head motion on BP and DAR estimation. Results: Changes in position and orientation of the striatum during the PET scans were observed before the head motion correction. BP values at pre-task condition were not changed significantly after the intra-condition registration. However, the BP values during and after the task and DAR were significantly changed after the correction. SPM analysis also showed that the extent and significance of the BP differences were significantly changed by the head motion correction and such changes were prominent in periphery of the striatum. Conclusion: The results suggest that misalignment of MRI-based VOI and the striatum in PET images and incorrect DAR estimation due to the head motion during the PET activation study were significant, but could be remedied by the data-driven head motion correction.
To date, we have considered the theoretical views, the standpoint of states and the discourse within the international community such as the UN Committee on the Peaceful Uses of Outer Space(COPUOS) regarding the Air/Outer Space Boundary Question which is one of the first issues of UN COPUOS established in line with marking the starting point of Outer Space Area. As above mentioned, discussions in the United Nations and among scholars of within each state regarding the delimitation issue often saw a division between those in favor of a functional approach (the functionalists) and those seeking the delineation of a boundary (the spatialists). The spatialists emphasize that the boundary between air and outer space should be delimited because the status of outer space is a type of public domain from which sovereign jurisdiction is excluded, as stated in Article 2 of Outer Space Treaty. On the contrary art. I of Chicago Convention is evidence of the acknowledgement of sovereignty over airspace existing as an international customary law, has the binding force of which exists independently of the Convention. The functionalists, backed initially by the major space powers, which viewed any boundary demarcation as possibly restricting their access to space, whether for peaceful or non-military purposes, considered it insufficient or inadequate to delimit a boundary of outer space without obvious scientific and technological evidences. Last more than 50 years there were large development in the exploration and use of outer space. But a large number states including those taking the view of a functionalist have taken on a negative attitude. As the element of location is a decisive factor for the choice of the legal regime to be applied, a purely functional approach to the regulation of activities in the space above the Earth does not offer a solution. It seems therefore to welcome the arrival of clear evidence of a growing recognition of and national practices concerning a spatial approach to the problem is gaining support both by a large number of States as well as by publicists. The search for a solution to the problem of demarcating the two different legal regimes governing the space above Earth has undoubtedly been facilitated and a number of countries including Russia have already advocated the acceptance of the lowest perigee boundary of outer space at a height of 100km. As a matter of fact the lowest perigee where space objects are still able to continue in their orbiting around the earth has already been imposed as a natural criterion for the delimitation of outer space. This delimitation of outer space has also been evidenced by the constant practice of a large number of States and their tacit consent to space activities accomplished so far at this distance and beyond it. Of course there are still numerous opposing views on the delineation of a outer space boundary by space powers like U.S.A., England, France and so on. Therefore, first of all to solve the legal issues faced by the international community in outer space activities like delimitation problem, there needs a positive and peaceful will of international cooperation. From this viewpoint, President John F. Kennedy once described the rationale behind the outer space activities in his famous "Moon speech" given at Rice University in 1962. He called upon Americans and all mankind to strive for peaceful cooperation and coexistence in our future outer space activities. And Kennedy explained, "There is no strife, ${\ldots}$ nor any international conflict in outer space as yet. But its hazards are hostile to us all: Its conquest deserves the best of all mankind, and its opportunity for peaceful cooperation may never come again." This speech seems to even present us in the contemporary era with ample suggestions for further peaceful cooperation in outer space activities including the delimitation of outer space.
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