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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.

Probabilistic Prediction and Field Measurement of Column Shortening for Tall Building with Bearing Wall System (초고층 내력벽식 구조물의 기둥축소량에 대한 확률론적 예측 및 현장계측)

  • Song, Hwa-Cheol;Yoon, Kwang-Sup
    • Journal of the Korea Concrete Institute
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    • v.18 no.1 s.91
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    • pp.101-108
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    • 2006
  • Accurate prediction of time-dependent column shortening is essential for tall buildings in both strength and serviceability aspects. The uncertainty associated with assumed values for concrete properties such as strength, creep, and shrinkage coefficients should be considered for the prediction of time-dependent column shortening of tall concrete buildings. In this study, the column shortenings of 41-story tall concrete building are predicted using monte carlo simulation technique based on the probabilistic analysis. The probabilistic column shortenings considering confidence intervals are compared with the actual column shortenings by field measurement. The time-dependent strains measured at tall bearing wall building were generally lower than the predicted strains and the measured values fell within a range ${\mu}-1.64$, confidence level 90%.

Mapping the Polarization of the Radio-Loud Lyman Alpha Nebula B3 J2330+3927

  • Yang, Yujin;You, Chang;Zabludoff, Ann;Smith, Paul;Jannuzi, Buell;Prescott, Moire
    • The Bulletin of The Korean Astronomical Society
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    • v.40 no.2
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    • pp.28.3-29
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    • 2015
  • $Ly{\alpha}$ nebulae, or "$Ly{\alpha}$ blobs", are extended (~100 kpc), bright (L[$Ly{\alpha}$] ~ 1044 erg/s) clouds of $Ly{\alpha}$-emitting gas. The origin of the $Ly{\alpha}$ emission remains unknown, but recent theoretical work suggests that measuring the polarization could discriminate among powering mechanisms. we will discuss current status of $Ly{\alpha}$ polarization observations at high-redshift and our on-going survey program. We will present the first narrow-band, imaging polarimetry of a $Ly{\alpha}$ blob, B3 J2330+3927 at z=3.09, with an embedded, radio-loud AGN (C. You et al. in prep.). The AGN lies near the blob's $Ly{\alpha}$ emission peak and its radio lobes align roughly with the blob's semi-major axis. With the SPOL polarimeter on the MMT telescope, we map the polarization in a grid of circular apertures of radius 0.6" (4.4 kpc), detecting a significant (>$2{\sigma}$) polarization fraction P% in 10 apertures and achieving strong upper-limits (as low as 2%) elsewhere. The degree of the polarization map increases from P% ~ 5% at ~5 kpc from the blob center to ~20% at the outer part (~30 kpc). The detections are distributed asymmetrically, roughly along the blob's major axis. The polarization angles (${\Theta}$) are mostly perpendicular to this axis. These results are consistent with the picture that $Ly{\alpha}$ photons produced at the AGN (or the host galaxy) are resonantly scattered away from the center. Higher polarization fraction on the radio jet suggests that the gas is more optically thin along the jet than the off-axis region.

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AKARI INFRARED CAMERA OBSERVATIONS OF THE 3.3 ㎛ PAH FEATURE IN Swift/BAT AGNs

  • Castro, Angel;Miyaji, Takamitsu;Shirahata, Mai;Ichikawa, Kohei;Oyabu, Shinki;Clark, David;Imanishi, Masatoshi;Nakagawa, Takao;Ueda, Yoshihiro
    • Publications of The Korean Astronomical Society
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    • v.32 no.1
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    • pp.197-199
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    • 2017
  • Using the InfraRed Camera (IRC) on board the infrared astronomical satellite AKARI we study the ${3.3{\mu}m}$ polycyclic aromatic hydrocarbon (PAH) feature and its connection to active galactic nucleus (AGN) properties for a sample of 54 hard X-ray selected bright AGN, including both Seyfert 1 and Seyfert 2 type objects. The sample is selected from the 9-month Swift/BAT survey in the 14-195 keV band and all of the sources have known neutral hydrogen column densities ($N_H$). The ${3.3{\mu}m}$ PAH luminosity ($L_{3.3{\mu}m}$) is used as a proxy for star-formation (SF) activity and hard X-ray luminosity ($L_{14-195keV}$) as an indicator of the AGN power. We explore for possible difference of SF activity between type 1 (un-absorbed) and type 2 (absorbed) AGN. We use several statistical analyses taking the upper-limits of the PAH lines into account utilizing survival analysis methods. The results of our log($L_{14-195keV}$) versus log($L_{3.3{\mu}m}$) regression shows a positive correlation and the slope for the type 1/unobscured AGN is steeper than that of type 2/obscured AGN at a $3{\sigma}$ level. Also our analysis shows that the circum-nuclear SF is more enhanced in type 2/absorbed AGN than type 1/un-absorbed AGN for low $L_{14-195keV}$ luminosity/low Eddington ratio AGN, while there is no significant dependence of SF activity on the AGN type in the high $L_{14-195keV}$ luminosities/Eddington ratios.

Crystal Structure of Nitrogen Adsorption of $Cd^{2+}$ ion Exchanged Zeolite-X (카드늄으로 이온교환된 제올라이트 X의 질소 흡착 결정구조)

  • Lee, Seok-Hee;Jeong, Gyoung-Hwa;Kim, Nam-Seok
    • Journal of the Korean Applied Science and Technology
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    • v.22 no.3
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    • pp.204-211
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    • 2005
  • The structure of nitrogen adsorption complex of fully dehydrated $Cd^{2+}$ ion exchanged zeolite-X, $|Cd_{46}(N)_{18}|[Si_{100}Al_{92}O_{384}]$, was determined in the cubic space group $Fd\overline{3}$ at 21(1) $^{\circ}C$ [a = 24.863(4) ] by single crystal X-ray diffraction analysis. The crystal was prepared by ion exchange in a flowing steam of 0.05 M aqueous solution $Cd(NO_3)_2$ : $Cd(O_2CCH_3)_2$ = 1:1 for five days, followed by dehydration at $500^{\circ}C$ and $2{\times}10^{-6}$ Tor. for two days, and exposured to 100 Tor. zeolitically dry nitrogen gas at 21(1) $^{\circ}C$. The structure was determined in atmosphere, and was refined within $F_0$ > $4{\sigma}(F_0)$ using reflection for which the final error can appear in indices $R_1$ = 0.097 and $wR_2$ = 0.150. In this structure, $Cd^{2+}$ ions occupied four crystallographic sites. Nine $Cd^{2+}$ ions filled the octahedral site I at the centers of hexagonal prisms (Cd-O = 2.452(16) ${\AA}$). Eight $Cd^{2+}$ ions filled site I' (Cd-O = 2.324(19) ${\AA}$). The remaining 29 $Cd^{2+}$ ions are found at two nonequivalent sites II (in the supercages) with occupancy of 11 and 18 ions. Each of these $Cd^{2+}$ ions coordinated to three framework oxygens, either at 2.159(15) or 2.147(14) ${\AA}$, respectively. Eighteen nitrogen molecules were adsorbed per unit cell and three per supercage.

A Comparison of Orbit Determination Performance for the KOMPSAT-2 using Batch Filter and Sequential Filter (아리랑위성 2호 데이터를 이용한 연속추정필터와 배치필터 처리 결과 비교)

  • Cho, Dong-Hyun;Kim, Hae-Dong
    • Aerospace Engineering and Technology
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    • v.11 no.2
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    • pp.149-157
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    • 2012
  • In this paper, the performance of the sequential filter for a space debris collision management system is analyzed by using the flight data of KOMPSAT-2. To analyze the performance of the sequential filter, the results of batch filter used in the orbit determination system of the KOMPSAT-2 ground station is used as reference data. The overlap method is also used to evaluate the orbit accuracy. This paper shows that the orbit determination accuracy of the sequential filter is similar to that of the KOMPSAT-2 ground station, but dissimilar characteristics exist due to the filter difference. In addition, it is also shown that the orbit determination accuracy is order of 1m root mean square by using 30 hour GPS navigation solutions and 6 hour comparison period for the overlap method.

Crystallographic analysis of dehydrated fully Tl+-exchanged zeolite Y

  • Lim, Woo Taik;Kwon, Ji Hye;Choi, Sik Young;Kim, Young Hun;Heo, Nam Ho
    • Analytical Science and Technology
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    • v.18 no.4
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    • pp.278-286
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    • 2005
  • The crystal structure of ($Tl_{71}$-Y ($Tl_{71}Si_{121}Al_{71}O_{384}$), ${\alpha}=24.706(3){\AA}$, dehydrated at 653 K and $8{\times}10^{-6}$ torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 294(1) K. The structure was refined using all intensities to the final error indices (using only the 302 reflection for which $F_{\circ}$ > $4{\sigma}(F_0)$) $R_1=0.0602$ (based on F) and $R_w=0.1744$ (based on $F_2$). The 71 $Tl^+$ ions per unit cell are found at four crystallographically distinct positions. Site I' position in the sodalite cavity opposite D6Rs are each occupied by eighteen $Tl^+$ ions per unit cell; these $Tl^+$ ions are recessed ca. $1.45{\AA}$ into the sodalite cavity from their O(3) plane (Tl-O=2.701(15), $3.163(16){\AA}$ and O-Tl-O=$92.1(4)^{\circ}$). The 23 $T1^+$ ions fill site II in the supercage; these $T1^+$ ions are recessed ca. $1.58{\AA}$ into the supercage from their O(2) plane (Tl-O = 2.850(16), $3.156(16){\AA}$ and O-T1-O = $85.1(5)^{\circ}$). The 19 $Tl^+$ ions lie at site III' in the supercage near a triple 4-ring (Tl-O = 3.10(7), $3.39(5){\AA}$ and O-Tl-O = 47.8(9), $95.3(18)^{\circ}$) and the remaining II ions occupy another site III' near a triple 4-ring in the supercage (Tl-O = 2.81(4), $2.71(4){\AA}$ and O-Tl-O = $57.3(8)^{\circ}$).

Two Crystal Structures of Ag+-and TI+-Exchanged Zeolite X, Ag27TI65-X and Ag23TI69-X

  • Kim, Soo-Yeon;Choi, Eun-Young;Kim, Yang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1759-1764
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    • 2002
  • Two crystal structures of dehydrated $Ag^+-andTl^+$-exchanged zeolite X$Ag_{27}Tl_{65-}X\;and\;Ag_{23}Tl_{69-}X$have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at 21(1) $^{\circ}C(a=24.758(4)\AAa=24.947(4)$, ${\AA}respectively).$, Their structures were refined to the final error indices $R_1$=0.055 and $wR_2$=0.057 with 375 reflections, and $R_1$=0.057 and $wR_2$=0.057 with 235 reflections, respectively, for which I > $3\sigma(I).$ In the structure of $Ag_{27}Tl_{65-}X,\;27\;Ag^+$ ions were found at two crystallographic sites: 15$Ag^+$ ions at site I at the center of the hexagonal prism and the remaining 12$Ag^+$ ions at site II' in the sodalite cavity. Sixty-five $Tl^+$ ions were located at three crystallographic sites: 20$Tl^+$ ions at site II opposite single six-rings in the supercage, 18$Tl^+$ ions at site I' in the sodalite cavity opposite the D6Rs, and the remaining 27$Tl^+$ ions at site III' in the supercage. In the structure of $Ag_{23}Tl_{69-}X$, 23$Ag^+$ ions were found at two crystallographic sites: 15 at site I and 8 at site II'. Sixty-nine $Tl^+$ ions are found at four crystallographic sites: 24 at site II, 17 at stie I', and the remaining 28 at two III' sites with occupancies of 22 and 6.

Suggestion of Charts and Equations Estimating the Strength Parameters of Rock Mass Using the Rock Mass Classification Value (RMC 값을 이용한 암반의 강도정수 값 추정도표 및 추정식의 제안)

  • Kim, Min-Kwon;Lee, Yeong-Saeng
    • Journal of the Korean Geotechnical Society
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    • v.30 no.3
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    • pp.73-85
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    • 2014
  • The strength parameters used in rock mass design are mainly estimated by equations using Hoek-Brown failure criterion because the tests to obtain the values are limited and expensive. To estimate the strength parameters, the Hoek-Brown failure criterion should be transformed to the Mohr-Coulomb failure criterion. But the processes are more or less cumbersome due to the several stages including the computation and the analyzing steps. In this study, several rock states of various conditions were modeled and then the strength parameters were estimated using the Hoek-Brown failure criterion. Thereafter by analyzing the results, some charts and equations estimating the strength parameters through only one step or easily in the field using the values of RMC, the uniaxial compressive strength and the rock constant ($m_i$), were suggested. And then the suggested method was compared and discussed with the existing method.

Single-Crystal Structure of |Li50Na25|[Si117Al75O384]-FAU

  • Kim, Hu Sik;Suh, Jeong Min;Kang, Jum Soon;Lim, Woo Taik
    • Journal of the Korean Chemical Society
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    • v.57 no.1
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    • pp.12-19
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    • 2013
  • The single-crystal structure of fully dehydrated partially $Li^+$-exchanged zeolite Y, ${\mid}Li_{50}Na_{25}{\mid}[Si_{117}Al_{75}O_{384}]$-FAU, was determined by single-crystal synchrotron X-ray diffraction techniques in the cubic space group $Fd\bar{3}m$ at 100(1) K. Ion exchange was accomplished by flowing stream of 0.1 M aqueous $LiNO_3$ for 2 days at 293 K, followed by vacuum dehydration at 623 K and $1{\times}10^{-6}$ Torr for 2 days. The structure was refined using all intensities to the final error indices (using only the 801 reflections with ($F_o$ > $4{\sigma}(F_o)$) $R_1/R_2=0.043/0.140$. The 50 $Li^+$ ions per unit cell are found at three different crystallographic sites. The 19 $Li^+$ ions occupy at site I' in the sodalite cavity: the $Li^+$ ions are recessed 0.30 ${\AA}$ into the sodalite cavity from their 3-oxygens plane (Li-O = 1.926(5) ${\AA}$ and $O-Li-O=117.7(3)^{\circ}$). The 20 $Li^+$ ions are found at site II in the supercage, being recessed 0.23 ${\AA}$ into the supercage (Li-O = 2.038(5) ${\AA}$ and $O-Li-O=118.7(3)^{\circ}$). Site III' positions are occupied by 11 $Li^+$ ions: these $Li^+$ ions bind strongly to one oxygen atom (Li-O = 2.00(8) ${\AA}$). About 25 $Na^+$ ions per unit cell are found at four different crystallographic sites: 4 $Na^+$ ions are at site I, 5 at site I', 12 at site II, and the remaining 4 at site III'.