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Catalytic Activities of Pd(II), Pd(I) and Pd(O)-diphosphine Complexes for Styrene Oxidation

  • Jo, Yeong Je;Kim, Gyeong Chae;Jeong, Jong Hwa;Park, Yu Cheol;Do, Myeong Gi
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.211-214
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    • 1995
  • The catalytic activities of palladium(0,Ⅰ,Ⅱ)-diphosphine complexes were investigated in styrene oxidation using H2O2 as terminal oxidant. The rates showed a dependence on the chelate ring patterns of complexes (PdCl2L); 5-membered ring (L=dppe: 1,2-bis(diphenylphosphino)ethane) < 6-membered ring (L=dppp: 1,3-bis(diphenylphosphino)propane) < 4-membered ring (L= dppm: bis(diphenylphosphino)methane). This sequence correlates with the ligand field strength and interactions between metal and phosphine ligands. Pd(Ⅱ,Ⅰ)-diphosphine complexes which are capable of making 4-membered chelate ring showed an enhancement of catalytic activities for styrene oxidation. The catalytic activities of Pd(0,Ⅰ,Ⅱ)-diphosphine complexes are described in terms of electronic and steric factors.

Study on Ginseng Protopanaxadiol and Protopanaxatriol Saponins-Induced Antinociception

  • Shin, Young-Hee;Kim, Seok-Chang;Han, Ji-Won;Kim, Dae-Hoon;Han, Sang-Sub;Shin, Dong-Ho;Nah, Seung-Yeol
    • The Korean Journal of Physiology and Pharmacology
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    • v.1 no.2
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    • pp.143-149
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    • 1997
  • We studied the effects of ginseng protopanaxadiol (PD) and protopanaxatriol (PT) saponins on the analgesia using several pain tests such as writhing, formalin, and tail-flick test. Using mouse, pretreatment of PD or PT saponins (i.p.) induced inhibition of abdominal constrictions caused by 0.9% acetic acid administration(i.p.). The $AD_{50}$ was around 27 (17-43) mg/kg for PD and 13.5 (3-61) mg/kg for PT saponins in writhing test. Both PD and PT saponins also showed the inhibition of bitings and lickings of hindpaw after administration of 1% formalin. In particular, both PD and PT saponins showed analgesic effects on second phase of pain. The $AD_{50}$ was 44.5 (26-76) mg/kg for PD and 105 (55-200) mg/kg for PT saponins in second phase of formalin test. For first phase pain inhibition by PD or PT saponins, they were required higher concentrations. However, PD saponins showed weak analgesic effects in tail-flick test with high concentration. In conclusion, we found that both PD and PT saponins have the analgesic effects in writhing test and second phase of pain in formalin test. These results suggest that both PD and PT saponins inhibit neurogenic or tonic pain rather than acute pain.

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Pd/Ge-based Emitter Ohmic Contacts for AlGaAs/GaAs HBTs (AlGaAs/GaAs HBT 에미터 전극용 Pd/Ge계 오믹 접촉)

  • Kim, Il-Ho
    • Korean Journal of Materials Research
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    • v.13 no.7
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    • pp.465-472
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    • 2003
  • Pd/Ge/Ti/Pt and Pd/Ge/Pd/Ti/Au ohmic contacts to n-type InGaAs were investigated for applications to AlGaAs/GaAs HBT emitter ohmic contacts. In the Pd/Ge/Ti/Pt ohmic contact minimum specific contact resistivity of $3.7${\times}$10^{-6}$ $\Omega$$\textrm{cm}^2$ was achieved by rapid thermal annealing at $^400{\circ}C$/10 sec. In the Pd/Ge/Ti/Au ohmic contact, minimum specific contact resistivity of $1.1${\times}$10^{-6}$ $\Omega$$\textrm{cm}^2$ was achieved by annealing at 40$0^{\circ}C$/10 sec but the ohmic performance was degraded with increasing annealing temperature due to the reaction between the ohmic contact materials and the InGaAs substrate. However, non-spiking planar interface and relatively good ohmic contact (high-$10^{-6}$ /$\Omega$$\textrm{cm}^2$) were maintained after annealing at $450^{\circ}C$/10 sec. Therefore, these thermally stable ohmic contact systems are promising candidates for compound semiconductor devices. RF performance of the AlGaAs/GaAs HBT was also examined by employing the Pd/Ge/Ti/Pt and Pd/Ge/Pd/Ti/Au systems as emitter ohmic contacts. Cutoff frequencies were 63.5 ㎓ and 65.0 ㎓, respectively, and maximum oscillation frequencies were 50.5 ㎓ and 51.3 ㎓, respectively, indicating very successful high frequency operations.

Electrical characteristics of GaAs MESFET according to the heat treatment of Ti/Au and Ti/Pd/Au schottky contacts (Ti/Au, Ti/Pd/Au 쇼트키 접촉의 열처리에 따른 GaAs MESFET의 전기적 특성)

  • 남춘우
    • Electrical & Electronic Materials
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    • v.8 no.1
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    • pp.56-63
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    • 1995
  • MESFETs of the Ti/Au and Ti/Pd/Au gate were fabricated on n-type GaAs. Interdiffusion at Schottky interfaces, Schottky contact properties, and MESFET characteristics with heat treatment were investigated. Ti of Ti/Au contact and Pd of Ti/Pd/Au contact acted as a barrier metal against interdiffusion of Au at >$220^{\circ}C$. Pd of Ti/Pd/Au contact acted as a barrier metal even at >$360^{\circ}C$, however, Ti of Ti/Au contact promoted interdiffusion of Au instead of role of barrier metal. As the heat treatment temperature increases, in the case of both contact, saturated drain current and pinch off voltage decreased, open channel resistance increased, and degree of parameter variation in Ti/Au gate was higher than in Ti/Pd/Au gate at >$360^{\circ}C$ Schottky barrier height of Ti/Au and Ti/Pd/Au contacts was 0.69eV and 0.68eV in the as-deposited state, respectively, and Fermi level was pinned in the vicinity of 1/2Eg. As the heat treatment temperature increases, barrier height of Ti/Pd/Au contact increased, however, decreased at >$360^{\circ}C$ in the case of Ti/Au contact. Ideality factor of Ti/Au contact was nearly constant regardless of heat treatment, however, increased at >$360^{\circ}C$ in the case of Ti/Au contact. From the results above, Ti/Pd/Au was stable gate metal than Ti/Au.

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The Application of Thera-band on Non-weight Bearing Leg Influence Hip Abductor Activities During Pelvic Drop Exercise in Patients With Gluteus Medius Weakness

  • Su-hwan Cha;Seok-hyun Kim;Seung-min Baik;Heon-seock Cynn
    • Physical Therapy Korea
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    • v.30 no.1
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    • pp.68-77
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    • 2023
  • Background: The weakness of the gluteus medius (GM) is associated with various musculoskeletal disorders. The increasing GM activity without synergistic dominance should be considered when prescribing pelvic drop exercise (PD). Isometric hip extension or flexion of the non-weight bearing leg using thera-band at the ankle during PD may influence hip abductor activities. Objects: To determine how isometric hip extension or flexion of the non-weight bearing leg using thera-band at the ankle during PD influences the activities of three subdivisions of GM (anterior, GMa; middle, GMm; posterior, GMp), tensor fasciae latae (TFL), contralateral quadratus lumborum (QL), and GMp/TFL, GMm/QL activity ratios in patients with GM weakness. Methods: Twenty-three patients with GM weakness were recruited. Three types of PD were performed: PD, PD with an isometric hip extension of the non-weight bearing leg (PDE), and PD with an isometric hip flexion of the non-weight bearing leg (PDF). Surface electromyography (SEMG) was used to measure hip abductor activities. One-way repeated-measures analysis of variance was used to assess the statistical significance of muscle activities and muscle activity ratios. Results: GMa, GMm, and GMp activities were significantly greater during PDF than during PD and PDE (p < 0.001, p = 0.001; p = 0.001, p = 0.005; p = 0.004, p = 0.004; respectively). TFL activity was significantly greater during PDE than during PD and PDF (p < 0.001, p < 0.001, respectively). QL activity was significantly greater during PDF than during PD (p = 0.003). GMp/TFL activity ratio was significantly lower during PDE than during PD and PDF (p = 0.001, p = 0.001, respectively). There were no significant differences in the GMm/QL activity ratio. Conclusion: PDF may be an effective exercise to increase the activities of all three GM subdivisions while minimizing the TFL activity in patients with GM weakness.

T-Cell Immunoglobulin Mucin 3 Expression on Tumor Infiltrating Lymphocytes as a Positive Prognosticator in Triple-Negative Breast Cancer

  • Byun, Kyung Do;Hwang, Hyo Jun;Park, Ki Jae;Kim, Min Chan;Cho, Se Heon;Ju, Mi Ha;Lee, Jin Hwa;Jeong, Jin Sook
    • Journal of Breast Cancer
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    • v.21 no.4
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    • pp.406-414
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    • 2018
  • Purpose: T-cell immunoglobulin and mucin domain-containing molecule 3 (TIM-3) is an emerging immune response molecule related to T-cell anergy. There has been tremendous interest in breast cancer targeting immune checkpoint molecules, especially in the triple-negative breast cancer (TNBC). This study was designed to investigate TIM-3 expression on tumor infiltrating lymphocytes (TILs), its relationships with clinicopathological parameters and expression of programmed death receptor 1 (PD-1)/programmed death receptor ligand 1 (PD-L1), and its prognostic role. Methods: Immunohistochemistry on tissue microarray blocks produced from 109 samples of invasive ductal carcinoma type TNBC was performed with antibodies toward TIM-3, PD-1, PD-L1 and breast cancer-related molecular markers. Associations between their expression and clinicopathological parameters as well as survival analyses were performed. Results: TIM-3 was expressed in TILs from all 109 TNBCs, consisting of 17 cases (<5%), 31 cases (6%-25%), 48 cases (26%-50%), and 13 cases (>51%). High TIM-3 was significantly correlated with younger patients (p=0.0101), high TILs (p=0.0029), high tumor stage (p=0.0018), high PD-1 (p=0.0001) and high PD-L1 (p=0.0019), and tended to be associated with higher histologic grade, absence of extensive in situ components and microcalcification. High TIM-3 expression was significantly associated with a combinational immunophenotype group of high PD-L1 and high PD-1 (p<0.0001). High TIM-3 demonstrated a significantly better disease-free survival (DFS) (p<0.0001) and longer overall survival (OS) (p=0.0001), together with high TILs and high PD-1. In univariate survival analysis, high TIM-3 showed reduced relapse risk (p<0.0001) and longer OS (p=0.0003), together with high PD-1 expression. In multivariate analysis, high TIM-3 was statistically significant in predicting prognosis, showing better DFS (hazard ratio [HR], 0.0994; 95% confidence interval [CI], 0.0296-0.3337; p=0.0002) and longer OS (HR, 0.1109; 95% CI, 0.0314-0.3912; p=0.0006). Conclusion: In this study, we demonstrate that TIM-3 expression is an independent positive prognostic factor in TNBC, despite its association with poor clinical and pathologic features.

Ammonia Conversion in the Presence of Precious Metal Catalysts (귀금속촉매하에서 암모니아의 전환반응)

  • Jang, Hyun Tae;Park, YoonKook;Ko, Yong Sig
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.806-812
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    • 2008
  • The ammonia decomposition reaction has been of increasing interest as a means of treating ammonia in flue gas in the presence of precious metal catalyst. Various catalysts, $Pt-Rh/Al_2O_3$, $Pt-Rh/TiO_2$, $Pt-Rh/ZrO_2$, $Pt-Pd/Al_2O_3$, $Pd-Rh/Al_2O_3$, $Pd-Rh/TiO_2$, $Pd-Rh/ZrO_2$, $Pt-Pd-Rh/Al_2O_3$, $Pd/Ga-Al_2O_3$, $Rh/Ga-Al_2O_3$, and Ru/Ga-$Al_2O_3$, were synthesized by using excess wet impregnation method. Using a homemade 1/4" reactor at $10,000{\sim}50,000hr^{-1}$ of space velocity in the presence of precious metal catalyst ammonia decomposition reactions were carried out to investigate the catalyst activity. The inlet ammonia concentration was maintained at 2,000 ppm, with an air balance. Both $T_{50}$ and $T_{90}$, defined as the temperatures where 50% and 90% of ammonia, respectively, are converted, decreased significantly when alumina-supported catalysts were applied. In terms of catalytic performance on the ammonia conversion in the presence of hydrogen sulfide, $Pt-Rh/Al_2O_3$ catalyst showed no effect on the poisoning caused by hydrogen sulfide. These results indicate that platinum-rhodium bimetallic catalyst is a useful catalyst for ammonia decomposition.

Synthesis of Carbocycles Using Metal Catalyst(I) -Stereoselective Synthesis of Cyclopentane Using Pd(0) Catalyst- (금속 촉매를 이용한 Carbocycle의 합성(I) -Pd(0) 촉매를 이용한 Cyclopentane의 입체선택적 합성-)

  • Suh, Young-Ger;Lee, Gi-Ho;Cho, Youn-Sang
    • YAKHAK HOEJI
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    • v.34 no.5
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    • pp.287-290
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    • 1990
  • An efficient stereoselective synthetic route to carbocycle is described. 1,1,2-Trisubstituted cyclopentane was synthesized from allylic carbonate by Pd(0) catalyzed cyclization.

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Palladium(II) Complexes of Aminophosphines (I). Characterization and Synthesis of $[Pd(L)X_2] with X = Cl^-, Br^-, I^-, NCS^-$ (아미노포스핀류를 포함하는 팔라듐 (II) 착물 (제1보). $[Pd(L)X_2] (X = Cl^-, Br^-, I^-, NCS^-)$의 합성과 성질)

  • Myung-Ki Doh;Bong-Gon Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.4
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    • pp.255-261
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    • 1983
  • Several new $[Pd(L)X_2]$ complexes have been prepared with aminophosphines (L) such as trans-1,2-bis[diphenylphosphino)amino]cyclohexane and 1,2-bis[(diphenylphosphino) amino] propane that contain phosphorus atom as ${\pi}$-electron acceptor, and the bond character of complexes have been investigated by means of infrared and electronic spectroscopy. It was found that thiocyanate ions are N-coordinated possibly due to the steric and electronic influence of the phosphorus atom in aminophosphines that formed seven-membered chelate rings, and that spectrochemical series that is derived from the electronic spectra of the complexes is $NCS^- > Cl^- > Br^- > I^-$

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Magnetic Properties and Relaxation of Vanadium Monolayer on Pd(001) Surface

  • Landge, Kalpana K.;Bialek, Beata;Lee, Jae-Il
    • Journal of Magnetics
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    • v.15 no.2
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    • pp.45-50
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    • 2010
  • We investigated the magnetism of vanadium monolayers on a Pd(001) surface. The electronic structure and the magnetic properties of the V/Pd(001) system were determined with the use of the full-potential linearized augmented plane-wave method within the general gradient approximation. Three magnetic configurations were studied: non-, ferro-, and antiferromagnetic. From the total energy calculations, we found that the V/Pd(001) system is the most stable in the antiferromagnetic configuration. The importance of relaxation on the magnetic properties of the systems was also studied. It was found that the Pd(001) surface covered with a V monolayer undergoes considerable relaxation in which the spacing between Pd layers increases in all three magnetic configurations. Contrary to the Pd interlayer spacing, the distance between the V overlayer and the topmost Pd layer is reduced. The interlayer spacing between the V overlayer and the Pd surface layer is the largest for the antiferromagnetic configuration. In the relaxed antiferromagnetic structure, the magnitude of the calculated magnetic moments on the V atoms was $1.31\;{\mu}_B$. The presence of the vanadium monolayer does not affect the paramagnetic properties of the Pd(001) surface.