• Nuclear Engineering and Technology
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• 제53권3호
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• pp.894-900
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• 2021

This paper examines sorption of Pd(II) onto illite, MX-80 bentonite, and Queenston shale in Na-Ca-Cl solutions of varying ionic strength (IS) from 0.01 to 6.0 mol/L (M) and pH_c ranging from 3 to 9 under atmospheric conditions. A 2-site protolysis non-electrostatic surface complexation and cation exchange model was applied to the Pd sorption onto illite and MX-80 using PHREEQC, and the model results were compared to the experimental ones obtained in this work. Surface complexation and cation exchange constants were estimated for both illite and MX-80 through the optimization process to bring the predicted distribution coefficients from the model into alignment with the experimentally derived values. These optimized surface complexation constants were compared to existing linear free energy relationships (LFER).

• Bulletin of the Korean Chemical Society
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• 제16권3호
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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.

• Bulletin of the Korean Chemical Society
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• 제18권2호
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• pp.218-221
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• 1997

When phenylation of styrene was carried out in the presence of Pd(OAc)2 and PPh3 in benzene, trans-stilbene was obtained in good yield (566%) with high selectivity (98%) under mild condition (55 ℃, 50 psi O2, 20 h). Since trans-stilbene could be produced not only from benzene but also from phenyl group of PPh3 by migration of its phenyl group to Pd, the competitiveness of benzene and the migratory aptitude of aryl group of triarylphosphine toward styrene has been investigated with various phosphines (PR3: P(p-C6H4CH3)3, P(p-C6H4OCH3)3, P(p-C6H4F)3, P(p-C6H4Cl)3, P(C6H5)3, P(C6H11)3, P(OC4H9n)3, P(CH2C6H5)3 and P(C6F5)3). The yield and selectivity toward trans-stilbene are increased as the basicity of the phosphines increases. The composition of arylated olefin from arylphosphine, in turn, increases as the electronegativity of the substituent on the aryl group of arylphosphines increases.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.235-237
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• 1986

Reaction of $(E)-{\beta}-chloro-{\gamma}$-hydroxyvinylmercurials, prepared by mercuration of propargyl alcohol and 2-methyl-3-butyne-2-ol, with olefins in the presence of a catalytic amount of $Li_2PdCl_4$ and 2 equiv of cupric chloride in methanol at $50^{\circ}C$ gave the corresponding (E,E)-2,4-dienols in moderate yields. However, addition of 1 equiv of inorganic bases such as magnesium oxide to the reaction mixture brings a rapid and clean vinylation and gave high yields of the dienols at room temperature. In the case of hindered (E)-2-chloro-3-chloromercuri-2-buten-1,4-diol prepared from 2-butyne-1,4-diol, reaction with olefins gave the dienols only in low yields even in the presence of 2 equiv of magnesium oxide.

• Bulletin of the Korean Chemical Society
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• 제8권4호
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• pp.246-250
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• 1987

The reaction of aryl iodides or bromides with olefins in the presence of 1 mol % of $PdCl_2(PPh_3)_2$ and 3 equiv. of $n-Bu_3N\; at\; 100^{\circ}C$ in carbon monoxide atmosphere gave the corresponding aryl vinyl ketones in good yields with small amount of vinylated 1-aryl olefins. But, when the reaction was proceeded under the 10 atm of carbon monoxide, aryl vinyl ${\alpha}$-diketones and aryl vinyl ketones were obtained in moderate to good yields. The reaction was tolerant of a wide variety of functional groups on either the aryl halides or olefin compounds. Reactivity of aryl halide decrease in the order; aryl iodide > aryl bromide ${\gg}$aryl chloride. In general, the reaction proceeded well and gave good yields of aryl vinyl ketones and aryl vinyl ${\alpha}$-diketones when reactants are substituted with electron withdrawing groups.

• 대한약학회:학술대회논문집
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• 대한약학회 2003년도 Proceedings of the Convention of the Pharmaceutical Society of Korea Vol.2-2
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• pp.182.3-183
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• 2003

(-)-Antofine is phenanthroindolizidine alkaloid being isolated from Cynanchum vincetoxicum. It has powerful cytotoxicity toward drug-sensitive KB-3-1 and multidrug resistant KB-V1 cancer cell line. We have successfully accomplished stereoselective total synthesis by using palladium catalyzed Stille coupling of l0-bromomethyl-2,3 ,6-trimethoxy-phenanthrene and (R)-(E)-4-(tributylstannanyl)but-3-en-2-o1, Overmann rearrangement of imidate, and RCM(ring-closing metathesis) for construction of pyrrolidine.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1746-1750
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• 2007

The second-order scattering (SOS) phenomenon of the interaction of Pd nanoparticles with protein was reported and a simple, sensitive, palladium nanoparticle-based assay for trace amount of protein with SOS technique was developed. The SOS intensities were significantly enhanced due to the interaction of Pd nanoparticles with bovine serum albumin (BSA) or human serum albumin (HSA) at pH 3.5 or 4.0, respectively. The maximum SOS peak appeared at 260/520 nm (λex/λem). The optimal experiment conditions, affecting factors and the influence of some coexisting substances were checked. The SOS intensity increased proportionally with the increase of Pd concentration below 3.0 × 10?5 mol·L?1, while declined gradually above 4.0 × 10?5 mol·L?1. BSA within the range of 0.01-2.6 μg·mL?1 and HSA of 0.01-1.7 μg·mL?1 can be detected with this method and the detection limits were 2.3 and 11.2 ng·mL?1, respectively. The method was successfully applied to the quantitative detection of total protein content in human serum samples with the maximum relative standard deviation (RSD) lower than 2.6% and the recoveries over the range of 99.5-100.5%.

• 대한화학회지
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• 제46권1호
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• pp.57-63
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• 2002

CTA(crude terephthalic acid)의 수소화 정제 반응이 고온의 회분식반응기에서 PdRu/CCM(carbon-carbonaceous composite material) 촉매 상에서 수행되었다. 반응 시간에 따른 In(4-CBA; 4-carboxybenzaldehyde)의 의존도가 선형성을 보임에서 수소화 정제는 1차 속도론을 따름을 알 수 있었다. 촉매량에 따른 반응 속도의 선형성에서 조사된 반응 조건은 정제 반응을 잘 대변할 수 있음을 알 수 있었다. 반응 전환율이 증가하면(4-CBA가 감소하면) 고체 및 액체의 p-toluic acid(p-tol)의 농도는 증가하였으나 벤조산(BA)의 농도는 크게 변하지 않았다. 4-CBA 농도가 대략 0.15% 이하일 때에는 PTA의 AT(alkalitransmittance)는 4-CBA농도에 반비례하며 이는 4-CBA의 수소화에 따라 발색물질도 제거 됨을 보여 준다. 4-CBA농도가 약 0.2% 이상이면 AT는 일정하였는데 이는 4-CBA 자체는 발색 효과를 가지지 않음을 보여준다. (0.3%Pd-0.2%Ru)/CCM 촉매는 0.5%Pd/C 상업 촉매에 비해 초기 활성은 낮으나, 상업 공장 반응기에서 사용한 후에는 오히려 큰 잔존 활성을 보였고 PdRu/CCM 촉매는 루테늄 함량이 약 $0.2{\sim}0.35%$ 일 때 활성의 상승효과를 보였다. PdRu/CCM 촉매는 0.5%Pd/C 상업 촉매를 대체할 가능성이 높음을 알 수 있다.

• 대한치과보철학회지
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• 제17권1호
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• pp.23-34
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• 1979

In this study, the adhesive strength of three commercial polycarboxylate cements to ten types of dental casting alloys, such as gold, palladium, silver, indium, copper, nickel, chromium, and human enamel and dentine were measured and compared with that of a conventional zinc phosphate cement. The $8.0mm{\times}3.0mm$ cylindrical alloy specimens were made by casting. The enamel specimens were prepared from the labial surface of human upper incisor, and the dentine specimens were prepared from the occulusal surface of the human molar respectively. Sound extracted human teeth, which had been kept in a fresh condition since, extraction, were mounted in a wax box with a cold-curing acrylic resin to expose the flattened area. The mounted teeth were then placed in a Specimen Cutter (Technicut) and were cut down under a water spray, and then the flat area on the all specimens were ground by hand with 400 and 600 grit wet silicone carbide paper. Two such specimens were then cemented together face-to-face with freshly mixed cement, and moderate finger pressure was applied to squeeze the cement to a thin and uniform film. All cemented specimens were then kept in a thermostatic humidor cabinet regulated at $23{\pm}2^{\circ}C.$ and more than 95 per cent relative humidity and tested after 24 hours and 1 week. Link chain was attached to each alloy specimen to reduce the rigidity of the jig assembly, and then all the specimens were mounted in the grips of the Instron Universal Testing Machine, and a tensile load was delivered to the adhering surface at a cross head speed of 0.20 mm/min. The loads to which the specimens were subjected were recorded on a chart moving at 0.50 mm/min. The adhesive strength was determined by measuring the load when the specimen separated from the cement block and by dividing the load by the area. The test was performed in a room at $23{\pm}2^{\circ}C.$ and $50{\pm}10$ per cent relative humidity. A minimum of five specimens were tested each material and those which deviated more than 15 per cent from the mean were discarded and new specimens prepared. From the experiments, the following results were obtained. 1) It was found that the adhesive strength of the polycarboxylate cement to all alloys tested was considerably greater than that of the zinc phosphate cement. 2) The adhesive strength of the polycarboxylate cements was superior to the non precious alloys, such as the copper, indium, nickel and chromium alloys, but it was inferior to the precious gold, silver and palladium alloys. 3) Surface treatment of the alloy was found to be an important factor in achieving adhesion. It appears that a polycarboxylate cement will adhere better to a smooth surface than to a rough one. This contrasts with zinc phosphate cements, where a rough helps mechanical interlocking. 4) The adhesion of the polycarboxylate cement with enamel was found superior to its adhesion with dentine.

• Nuclear Engineering and Technology
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• 제24권2호
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• pp.141-153
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• 1992

상온핵융합의 실험적 검증을 위하여 가공조건 및 기하학적조건이 다른 7종류의 팔라디움전극을 사용하여 24~28시간, 전류밀도 83~600 mA/$\textrm{cm}^2$의 조건하에 전기분해를 실시하였다. 상기조건 하에서 삼중수소의 농축에 기인한 분리팩타(separation factor)를 측정하였고 핵융합의 부산물일수도 있는 삼중수소 증가량을 측정하였다. 또한 초과열 계 산과 관련된 K(net Faradic efficiency)를 측정하여 산소/중수소 가스의 재결합정도를 조사하였다. 양전자소멸측정장치 및 일정체적 가스주입장치를 이용하여 팔라디움전극에서 격자결함과 수소의 반응 및 거동에 대하여 조사하였다. 전기분해하는 동안 삼중수소 농축현상이 관찰되었으나 핵융합의 증거가 될만한 삼중수소양은 검출되지 않았다. 한편 산소/수소 가스의 재결합 정도는 32%로 나타났다. 이는 재결합과정이 발열반응이므로 전기분해과정에서 핵반응과 관계없이 초과엔탈피가 발생할 수 있음을 의미한다. 양전자소멸측정장치를 이용하여 양전자수명, 양전자소멸밀도, P/W 및 R 파라메터의 측정을 통하여 전극의 격자결함(전위 및 공공)에 수소가 집적 (trap)되며 수소집적은 공공에서 보다 전위에 약간 더 선호하는 것으로 나타났다. 전극의 수소화물형성에 수반하여 대부분 전위가 발생한 것으로 나타났다. 또한 팔라디움수소화물의 등시소둔실험을 통하여 소량의 미소공동 형태의 결함이 존재하는 것으로 추정하였고 그 결함의 크기는 수 $\AA$정도인 것으로 생각된다.