• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.986-990
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• 2004

Condensation of salicylaldehyde $(2-HOC_6H_4C(O)H)$ with allylamine afforded the unsaturated salicylaldimine, $2-HOC_6H_4C(H)=NCH_2CH=CH_2$. Similar reactivity was observed with substituted salicylaldehydes. Further reaction of these Schiff bases with palladium acetate or $Na_2PdCl_4$ afforded complexes of the type $PdL_2$, where L = deprotonated Schiff base. The molecular structure of the parent salicylaldimine palladium complex $[trans-(2-OC_6H_4C(H)=NCH_2CH=CH_2)_2Pd]$ (1) was characterized by an X-ray diffraction study. Crystals of 1 were monoclinic, space group $P2_1/n,\;a\;=\;14.0005(9)\;{\AA},\;b\;=7.2964(5)\;{\AA},\;c\;=\;17.5103(12)\;{\AA},\;{\beta}\;=\;100.189(1)^{\circ}$, Z = 4. Analogous chemistry with 4-vinylaniline also gave novel palladium complexes containing a pendant styryl group. Crystals of $[trans-(2-HOC_6H_4C(H)=N-4-C_6H_4CH=CH_2)_2Pd]$ (4) were monoclinic, space group $P2_1/c$, a = 13.7710(14) ${\AA}$, b = 11.0348(11) ${\AA}$, c = 7.8192(8) ${\AA}$, ${\beta}\;=\;98.817(2)^{\circ}$, Z = 2.

• Asian Pacific Journal of Cancer Prevention
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• v.13 no.8
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• pp.4031-4036
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• 2012

Background: The negative signaling provided by interactions of the co-inhibitory molecule, programmed death-1 (PD-1), and its ligands, B7-H1 (PD-L1) and B7-DC (PD-L2), is a critical mechanism contributing to tumor evasion; blockade of this pathway has been proven to enhance cytotoxic activity and mediate antitumor therapy. Here we evaluated the anti-tumor efficacy of AAV-mediated delivery of the extracellular domain of murine PD-1 (sPD-1) to a tumor site. Material and Methods: An rAAV vector was constructed in which the expression of sPD-1, a known negative regulator of TCR signals, is driven by human cytomegalovirus immediate early promoter (CMV-P), using a triple plasmid transfection system. Tumor-bearing mice were then treated with the AAV/sPD1 construct and expression of sPD-1 in tumor tissues was determined by semi quantitative RT-PCR, and tumor weights and cytotoxic activity of splenocytes were measured. Results: Analysis of tumor homogenates revealed sPD-1 mRNA to be significantly overexpressed in rAAV/sPD-1 treated mice as compared with control levels. Its use for local gene therapy at the inoculation site of H22 hepatoma cells could inhibit tumor growth, also enhancing lysis of tumor cells by lymphocytes stimulated specifically with an antigen. In addition, PD-1 was also found expressed on the surfaces of activated CD8+ T cells. Conclusion: This study confirmed that expression of the soluble extracellular domain of PD-1 molecule could reduce tumor microenvironment inhibitory effects on T cells and enhance cytotoxicity. This suggests that it might be a potential target for development of therapies to augment T-cell responses in patients with malignancies.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2711-2716
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• 2011

para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)($OC_6H_4$-p-X) (NCN = 2,6-$(CH_2NMe_2)_2C_6H_3$; X = $NO_2$ (1), Me (2)) were prepared by the reaction of Pd(NCN)($OSO_2CF_3$) with equi-molar amount of $NaOC_6H_4$-p-X. Treatment of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4$-p-Me affords the hydrogen-bonding adduct complex 3 ($2{\cdot}HOC_6H_4$-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free $HOC_6H_4$-p-Me. Complex 1 does not undergo adduct formation with $HOC_6H_4-p-NO_2$ neither from metathesis reaction of Pd(NCN)($OSO_2CF_3$) with an excess amount of $NaOC_6H_4-p-NO_2$ nor from treatment of 1 with free $HOC_6H_4-p-NO_2$. Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes ${\sigma}$-ligand exchange reaction with $HOC_6H_4-p-NO_2$ to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective $pK_a$ values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product $PhOC_6H_4$-p-Me which was identified by GC/MS spectroscopy.

• Proceedings of the KIEE Conference
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• 1998.07d
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• pp.1478-1480
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• 1998

Inception and propagation of electrical tree and properties of partial discharge(PD) pulses accompanying with tree in low density polyethylene were discussed. We observed the characteristics of process of electrical tree by using optical microscope and investigated the statistical characteristics of the PD pulses by analyzing PD quantities and distribution patterns. The PD pulses were analyzed by q-n, $\phi$-n and $\phi$-q distribution. The statistical operators used were skewness(s), kurtosis(k) and average phase angle. The skewness and average discharge phase angle of PD pulses increased as the Propagation of tree. The kurtosis was about 1.8 at the Inception of tree, but It increased as the propagation of tree.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.05a
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• pp.704-707
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• 1999

Partial discharge(PD) in air insulated electric power systems is responsible for considerable power lossesfrom high voltage transmission lines. PD in air often leads to deterioration of insulation by the combined action of the discharge ions bombarding the surface and the action of chemical compounds that are formed by the discharge and may give rise to interference in ommunication systems. PD can indicate incipient failure. Thus understanding and classification of PD in air is very important to discern source of PD. In this paper, we investigated PD in air by using statical method. We classified air discharge with corona, surface discharge and cavity discharge by source of discharge. we used the mean pulse-height phase distribution $H_{qmean}(\psi)$, the max pulse-height phase distribution $H_{qmax}(\psi)$ , the pulse count phase distribution $H_n(\psi)$ and the max pulse height vs. repetition rate $H_{q}(n)$ for analysis PD pattern. We used statistical operators, such as skewness(S+. S-1, kurtosis(K+, K-), mean phase(AP+. AP-), cross-correlation factor(CC) and asymmetry from the distribution.

• Applied Chemistry for Engineering
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• v.33 no.3
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• pp.302-308
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• 2022

The PdO nanoparticle with large surface area was selected to solve the environmental pollution problem at fire range caused by high energy explosives research department explosive (RDX) and high melting explosive (HMX). By simulating water pollution, RDX and HMX nitramine explosives were dissolved in water, followed by the degradation reaction at 313 K by adding PdO. In order to measure the degradation reaction rate of explosives, ¹H NMR was used, which can monitor the reaction rate without losing sample during reaction, and observe the progress of the reaction through the spectrum. The results showed that the degradation of RDX and HMX by PdO nanoparticles are pseudo-first order reaction. The degradation of explosives compounds were observed via the chemical shift and peak intensity analysis of NMR peaks. The measured rate constants for these reactions of RDX and HMX were 2.10 × 10^-2 and 6.35 × 10^-4 h^-1, respectively. This study showed that the application of PdO nanoparticles for explosives degradation is a feasible option.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.44-50
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• 1992

The ability to account for magnetic and spectra properties of complexes was investigated for the splitting of the degenerate d-orbitals and with nonaqueous solution by UV/vis-spectrophotometric method. The correlation of the magnetitude of 10Dq obtained from the spectra, the pairing energy, and the spin state of the complexes. The electrochemical behavior of complexes were investigated by the use of cyclic voltammetry in aprotic media. These reduction peak of $[(C_6H_5)3_P]_2Pd(II)(CH_3COO)_2$ and $[(C_6H_5)_3Pd]_2Pd(II)Cl_2$ were irreversible one-electron processes at peak $E_{pc1} = -1.32 V,\;E_{pc2} = -1.56 V$ and $E_{pc1} = -1.74 V,\;E_{pc2} = -1.88 V$ of these complexes vs. Ag/AgCl, but nickel complexes were not to be reducible.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.679-684
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• 1992

New Pd(IV) complexes have been prepared through the reactions of $trans-[Pd(en)_2Cl_2](ClO_4)_2 $(en = ethylenediamine) with Guanine, Adenine, or Uracil anion as purine and pyrimidine base. We identified the ratio of central metal versus ligands by $C{\cdot}H{\cdot}N$ elemental analysis and proposed the coordinating site of the base by infrared spectrum, $^1H-NMR,\; and\; ^{13}C$-NMR spectrum. Guanine or Adenine ligand coordinated at N7 site and an en ligand exchanged for $ClO_4^-$ counter ions of the starting material . As these results, the complexes showed the formula $[Pd(en)L_2(ClO_4)_2](ClO_4)_2{\cdot}(en)$, (L = Guanine, Adenine). But in the Uracil complex no exchange of the en ligand and $ClO_4^-$ occured and Uracil anion preferred the N1 to N3 as coordinating site, the complex $[Pd(en)_2(Urac)_2](ClO_4)_2(Urac = Uracil anion).$

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.685-691
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• 1992

The $d^8$-transition metal complexes containing diphosphine, $MCl_2PP$ were prepared by using $K_nMCl_m$ as starting materials, wherein M were Ni(II), Pd(II), Pt(II) and Au(III) and PP were bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) and bis(diphenylphosphino)ethylene(dppety). The complexes were characterized by the spectral property $(^H-NMR$, $^{31}P-NMR$ and UV-Visible spectra) together with elemental analysis. The complexes were tested for the catalytic activity on the formation reactions of 3(2H)-furanone and cyclic carbonate. The only Ni(II)- and Pd(II)-diphosphine complexes displayed a good catalytic effects in the production of 3(2H)-furanone from 2-methyl-3-butyn-2-ol [reaction (1)]. But all the diphosphine complexes as catalyst were almost inactive towards cyclic carbonate production preaction [reaction (2)].

• Korean Journal of Crystallography
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• v.15 no.2
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• pp.74-77
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• 2004

The crystal structure of Dinitroethylenediaminepalladium(II), $Pd(C_2H_8N_2)(NO_2)_2$, has been determined by X-ray crystallography. Crystal data: a=7.425(3), b=8.480(4), c=11.885(2) ${\AA}$, Orthorhombic, $A2_1ma$ (Space Group No=36), Z=4, V=748.3(4) ${\AA}^3,\;D_c=2.295 gcm^{-3},\;{\mu}=2.457mm^{-1}$. The structure was solved by Patterson method and refined by full matrix least-square methods using unit weights. The final R and S values were $R_1=0.0306,\;R_w=0.0802,\;R_{all}=0.0320,\;and\;S=1.166)$ for the observed 377 reflections. Bond lengths and angles of palladium complex are similar to the previously reported data. The complex structure is one dimensional Reiset's salt type analogue showing zigzag chain of Pd-Pd length and angle of 3.762(2) ${\AA}$ and $161.41(5)^{\circ}$. The complex molecules are linked through inter-and intramolecular hydrogen bonds of 3.05(1) and 3.15(1) ${\AA}$ between oxygen and nitrogen.