• Title/Summary/Keyword: late transition metal

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Novel solvothermal approach to hydrophilic nanoparticles of late transition elements and its evaluation by nanoparticle tracking analysis

  • Dutilleul, Marion Collart;Seisenbaeva, Gulaim A.;Kessler, Vadim G.
    • Advances in nano research
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    • v.2 no.2
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    • pp.77-88
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    • 2014
  • Solvothermal treatment of late transition metal acetylacetonates in a novel medium composed either of pure acetophenone or acetophenone mixtures with amino alcohols offers a general approach to uniform hydrophilic metal nanoparticles with high crystallinity and low degree of aggregation. Both pure metal and mixed-metal particles can be accesses by this approach. The produced materials have been characterized by SEM-EDS, TEM, FTIR in the solid state and by Nanoparticle Tracking Analysis in solutions. The chemical mechanisms of the reactions producing nanoparticles has been followed by NMR. Carrying out the process in pure acetophenone produces palladium metal, copper metal with minor impurity of $Cu_2O$, and NiO. The synthesis starting from the mixtures of Pd and Ni acetylacetonates with up to 20 mol% of Pd, renders in minor yield the palladium-based metal alloy along with nickel oxide as the major phase. Even the synthesis starting from a mixed solution of $Cu(acac)_2$ and $Ni(acac)_2$ produces oxides as major products. The situation is improved when aminoalcohols such as 2-aminoethanol or 2-dimethylamino propanol are added to the synthesis medium. The particles in this case contain metallic elements and pairs of individual metals (not metal alloys) when produced from mixed precursor solutions in this case.

Oligomerizations and Polymerizations of Olefins by Various Late Transition Metal Catalysts

  • Bahuleyan Bijal Kottukkal;Lee Kyoung-Ju;Son Gi-Wan;Choi Jae-Ho;Chandran Deepak;Abraham Sinoj;Ha Chang-Sik;Kim Il
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.155-155
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    • 2006
  • The most commercially and academically advanced catalysts of late transition metals are diimine complexes based on Pd(II)/Ni(II) and bis(imino)pyridyl complexes based on Fe(II)/Co(II). It is well known that the former systems yield branched polyethylenes and the latter linear PEs. In this presentation, effect of extremely bulky ligands with electron withdrawing/donating substituents at a remote position from Ni(II) metal center and of using multi-nuclear homo or hetero multi-metal on the ethylene polymerization is to be paged.

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Immobilization of Late Transition Metal Catalyst on the Amino-functionalized Silica and Its Norbornene Polymerization (아미노-기능화된 실리카 위 후전이 금속 촉매 담지 및 이를 이용한 노보넨 중합)

  • Pacia, Rose Mardie P.;Kim, So Hui;Lee, Jeong Suk;Ko, Young Soo
    • Applied Chemistry for Engineering
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    • v.27 no.3
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    • pp.313-318
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    • 2016
  • In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.

Structure-Property Relationship of Polynorbornene derivative

  • Shin, Boo-Gyo;Shin, Jin-Bok;Mulpuri Syamkumar V.;Yoon, Do, Y.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.349-349
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    • 2006
  • Vinyl-polynorbornene has good thermal stability, high transparency and low dielectric constant. However, it has low solubility, poor mechanical and adhesive properties. In this work, polynorbornene derivatives were prepared by Pd(II) late transition metal catalyst. The polymers have good solubility, and are thermally stable up to$300^{\circ}C$ The glass transition temperature is decreased as the side-chain becomes bulkier. Structure-property relationship of polynorbornene derivatives measured by X-ray scattering, mechanical and electrical properties will be discussed.

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Transition and social-cultural values of goldwork embroidery in Europe (유럽 골드워크 자수의 시대별 변천과 사회·문화적 가치)

  • Kim, Yi Rang;Kwon, Mi Jeong
    • The Research Journal of the Costume Culture
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    • v.28 no.4
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    • pp.544-561
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    • 2020
  • Goldwork embroidery is the art of embroidery using metal threads. As well as being used as a decorative element of religious clothing, flags, performing costumes, uniforms, and badges, goldwork embroidery is also used in many current designer collections. Therefore, this study aimed to examine the techniques and materials of goldwork embroidery and the formative characteristics and socio-cultural values of goldwork embroidery from its beginning to the early 20th century. For this study, various embroidery works, costumes, museum portraits, and literature were analyzed. The results are as follows. First, the transition of goldwork embroidery was divided into 4 categories: The beginning of goldwork embroidery; the golden age of goldwork embroidery; the maturity of goldwork embroidery; and various goldwork embroidery (depending on the materials used, usage, and design features). The earliest extant example is the "Maaseik fragments" in Belgium dating from the late 8th to early 9th centuries. Until the 15th century, the Church was the most important patron of goldwork embroidery; however, after the 15th century, goldwork embroidery was produced on costumes. Second, the social-cultural values of goldwork embroidery (based on transition and formative features) were classified as expression of divinity, instrument of governance, desire to be approved, and tools of self-expression. Through this study, it is evident that there have been many advances in both technique and technology over time. Furthermore, patterns of usage and social-cultural values of goldwork embroidery have changed significantly.

Glass Transition Temperature of Poly(methyl methacrylate) Obtained with Ferrocene-Based Diimine Pd(II) Catalyst (Ferrocene-Based Diimine Pd(II) 촉매로 얻은 폴리(메틸메타크릴레이트)의 유리전이온도)

  • 박태학;이동호;김태정;박동규
    • Polymer(Korea)
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    • v.26 no.3
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    • pp.410-414
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    • 2002
  • The late transition Pd catalyst of low oxophilicity that has ferrocene -based diimine ligand for stabilization of center metal had been synthesized and applied for the polymerization of methyl methacrylate (MMA). In the presence of triisobutylaluminium (TIBA) for impurity scavenger, the effects of polymerization temperature and [TIBA]/[Pd] mole ratio on the yield and glass transition temperature ($T_g$) of PMMA had been examined. For 40~$50^{\circ}C$ of polymerization temperature and 2000~3000 of [TIBA]/[Pd] mole ratio, higher polymer yields were obtained. It was observed that ($T_g$) of PMMA is almost independent to the polymerization temperature but influenced by the [TIBA]/[Pd] mole ratio. With the examination of($T_g$) of PMMA with the structure of polymer, it had been found that T$_{g}$ of PMMA exhibits a linear relationship with the isotacticity of polymer.r.

Polymerizations of Propylene with Unsymmetrical ($\alpha$-Diimine)nickel(II) Catalysts

  • Jeon Man-Seong;Han Chul-Jong;Kim Sang-Youl
    • Macromolecular Research
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    • v.14 no.3
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    • pp.306-311
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    • 2006
  • New unsymmetrical ($\alpha$-Diimine)nickel(II) catalysts having different pendent groups at the ortho positions on aromatic rings were synthesized and subjected to propylene polymerizations with MAO (methylaluminoxane). Structural analyses of the resulting polypropylenes by $^1H\;and\;^{13}C\;NMR$ showed that the ortho substituents on aromatic rings of ($\alpha$-diimine)nickel(II) catalyst affected significantly the polypropylene microstructure. While $C_s$ symmetric catalyst afforded a syndiotactic polypropylene (rr triad content=66%) due to the syndiospecific chain end control, $C_1$ symmetric catalysts produced much less stereoregular polypropylenes (rr triads content <50%), presumably because of collision of the isospecific site control with the syndiospecific chain end control.

Effect of B-Cation Doping on Oxygen Vacancy Formation and Migration in LaBO3: A Density Functional Theory Study

  • Kwon, Hyunguk;Park, Jinwoo;Kim, Byung-Kook;Han, Jeong Woo
    • Journal of the Korean Ceramic Society
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    • v.52 no.5
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    • pp.331-337
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    • 2015
  • $LaBO_3$ (B = Cr, Mn, Fe, Co, and Ni) perovskites, the most common perovskite-type mixed ionic-electronic conductors (MIECs), are promising candidates for intermediate-temperature solid oxide fuel cell (IT-SOFC) cathodes. The catalytic activity on MIEC-based cathodes is closely related to the bulk ionic conductivity. Doping B-site cations with other metals may be one way to enhance the ionic conductivity, which would also be sensitively influenced by the chemical composition of the dopants. Here, using density functional theory (DFT) calculations, we quantitatively assess the activation energies of bulk oxide ion diffusion in $LaBO_3$ perovskites with a wide range of combinations of B-site cations by calculating the oxygen vacancy formation and migration energies. Our results show that bulk oxide ion diffusion dominantly depends on oxygen vacancy formation energy rather than on the migration energy. As a result, we suggest that the late transition metal-based perovskites have relatively low oxygen vacancy formation energies, and thereby exhibit low activation energy barriers. Our results will provide useful insight into the design of new cathode materials with better performance.

Recent advances of aromatic C-F bond borylation and its application to positron emission tomography

  • Song, Dalnim;Lee, Sanghee;Lee, Byung Chul;Kim, Sang Eun;Lee, Eunsung
    • Journal of Radiopharmaceuticals and Molecular Probes
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    • v.1 no.2
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    • pp.80-87
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    • 2015
  • Carbon-fluorine (C-F) bonds have been found ubiquitously in pharmaceuticals, radiopharmaceuticals, agrochemicals, and material science due to their unique properties such as thermal and oxidative stability and lipophilicity to improve bioavailability. For the past five years, there have been significant advances in F-18 fluorination of aromatic complex molecules combined with the development of late-stage fluorination reactions. More recently, direct incorporation of F-18 to fluorinated aromatic molecules via borylation of C-F bonds has been developed by Niwa and Hosoya. In this minireview, we will discuss the progress of C-F bondborylation of fluorinated arenes utilizing transition metal catalysts and the impact on the development of F-18 radiotracers for positron emission tomography (PET).

Metal Surface Coating Using Electrospray of Biodegradable Polymers and $\alpha$-Lipoic Acid Release Behavior for Drug-Eluting Stents (생분해성 고분자의 전기분사를 이용한 약물방출 스텐트용 금속표면 코팅 및 ALA방출 거동)

  • Kim, Dong-Min;Lee, Bong-Soo;Park, Cheol-Ho;Park, Kwi-Deok;Son, Tae-Il;Jeong, Myeong-Ho;Han, Dong-Keun
    • Polymer(Korea)
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    • v.34 no.2
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    • pp.178-183
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    • 2010
  • Medical metal stents inserted to patients with a cardiovascular disease associated with coronary artery system have relatively increased the survival rate. The development of new stents is, however, urgently required due to restenosis and late thrombosis generated in metal stents. To solve these problems, the biodegradable polymers such as poly(lactide-co-glycolide) (PLGA), poly(L-lactide)(PLLA), and poly ($\varepsilon$-caprolactone)(PCL) were mixed with alpha lipoic acid (ALA), which is well known to inhibit the proliferation of neointimal hyperplasia. Subsequently, the ALA-loaded polymers were coated on stainless steel by electrospray. The drug-eluting behaviors from the coated polymers were investigated according to kinds and concentrations of polymers, spray rates, and kinds of solvents. The drug-eluting rate from PCL with the lowest glass transition temperature was the fastest among three polymers and followed by PLGA and PLLA. The surface roughness increased as the spray rate was increased and also the drug-eluting rate was affected by kinds of solvents with different boiling point. It is expected that drug-eluting stent (DES) coated with ALA-loaded polymers can be applied practically for clinical applications by controlling the behavior of drug release.