• Title/Summary/Keyword: O-O bond formation

검색결과 138건 처리시간 0.024초

Biological Inspiration toward Artificial Photostystem

  • Park, Jimin;Lee, Jung-Ho;Park, Yong-Sun;Jin, Kyoungsuk;Nam, Ki Tae
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.91-91
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    • 2013
  • Imagine a world where we could biomanufacture hybrid nanomaterials having atomic-scale resolution over functionality and architecture. Toward this vision, a fundamental challenge in materials science is how to design and synthesize protein-like material that can be fully self-assembled and exhibit information-specific process. In an ongoing effort to extend the fundamental understanding of protein structure to non-natural systems, we have designed a class of short peptides to fold like proteins and assemble into defined nanostructures. In this talk, I will talk about new strategies to drive the self-assembled structures designing sequence of peptide. I will also discuss about the specific interaction between proteins and inorganics that can be used for the development of new hybrid solar energy devices. Splitting water into hydrogen and oxygen is one of the promising pathways for solar to energy convertsion and storage system. The oxygen evolution reaction (OER) has been regarded as a major bottleneck in the overall water splitting process due to the slow transfer rate of four electrons and the high activation energy barrier for O-O bond formation. In nature, there is a water oxidation complex (WOC) in photosystem II (PSII) comprised of the earthabundant elements Mn and Ca. The WOC in photosystem II, in the form of a cubical CaMn4O5 cluster, efficiently catalyzes water oxidation under neutral conditions with extremely low overpotential (~160 mV) and a high TOF number. The cluster is stabilized by a surrounding redox-active peptide ligand, and undergo successive changes in oxidation state by PCET (proton-coupled electron transfer) reaction with the peptide ligand. It is fundamental challenge to achieve a level of structural complexity and functionality that rivals that seen in the cubane Mn4CaO5 cluster and surrounding peptide in nature. In this presentation, I will present a new strategy to mimic the natural photosystem. The approach is based on the atomically defined assembly based on the short redox-active peptide sequences. Additionally, I will show a newly identified manganese based compound that is very close to manganese clusters in photosystem II.

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Fabrication and Characterization of the Ti-TCP Composite Biomaterials by Spark Plasma Sintering

  • Mondal, Dibakar;Park, Hyun-Kuk;Oh, Ik-Hyun;Lee, Byong-Taek
    • 한국재료학회:학술대회논문집
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    • 한국재료학회 2011년도 춘계학술발표대회
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    • pp.53.2-53.2
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    • 2011
  • Ti metal has superior mechanical properties along with biocompatibility, but it still has the problem of bio-inertness thus forming weaker bond in bone/implant interface and long term clinical performance as orthopaedic and dental devices are restricted for stress shielding effect. On the other hand, despite the excellent biodegradable behavior as being an integral constituent of the natural bone, the mechanical properties of ${\beta}$-tricalcium phosphate $(Ca_3(PO_4)_2;\;{\beta}-TCP)$ ceramics are not reliable enough for post operative load bearing application in human hard tissue defect site. One reasonable approach would be to mediate the features of the two by making a composite. In this study, ${\beta}$-TCP/Ti ceramic-metal composites were fabricated by spark plasma sintering in inert atmosphere to inhibit the formation of $TiO_2$. Composites of 30 vol%, 50 vol% and 70 vol% ${\beta}$-TCP with Ti were fabricated. Detailed microstructural and phase characteristics were investigated by FE-SEM, EDS and XRD. Material properties like relative density, hardness, compressive strength, elastic modulus etc. were characterized. Cell viability and biocompatibility were investigated using the MTT assay and by examining cell proliferation behavior.

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Facile Modification of Surface of Silica Particles with Organosilanepolyol and Their Characterization

  • Lee, Joongseok;Han, Joon Soo;Yoo, Bok Ryul
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3805-3810
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    • 2013
  • The surface modification of silica particles (SPs) was systemically conducted by the treatment of 0.1-10 wt % phenylsilanetriol (PST) on the basis of SPs used through two step processes: 1) the PST coating of SPs via evaporation under reduced pressure and 2) their thermal condensation leading to Si-O-Si bond formation via heating at $130^{\circ}C$. The evaluation of the modified SPs was conducted by the simple floating test on water and the measurement of the contact angle (CA) of water droplet on the 2-dimensional layer of modified SPs on slide glass. When PST was used about 2 wt % or above on the basis of SPs (about average size: 50 nm) used, the modified SPs were fully floated on the water and all dispersed into upper organic solvent layer after a shaking with the mixture of the water and benzene, indicating that the modified SPs have hydrophobic properties. The modified SPs were characterized by $^{29}Si$ MAS NMR and physicochemical properties including SEM, TEM, BET, adsorption/desorption isotherms, etc. were measured and compared each other in details. This research demonstrates that the organosilanetriol is a good modifier applicable for the surface modification of inorganic oxide particles using a low amount of modifier on the basis of oxide particles used.

A Chromo- and Fluoroionophoric Thiaoxaaza-Macrocycle Functionalized with Nitrobenzofurazan Exhibiting Mercury(II) Selectivity

  • Lee, Ji-Eun;Lee, Shim-Sung;Choi, Kyu-Seong
    • Bulletin of the Korean Chemical Society
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    • 제31권12호
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    • pp.3707-3710
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    • 2010
  • A chromo/fluorogenic $NO_2S_2$-macrocycle L functionalized with nitrobenzofurazan unit as a dual-signaling probe was synthesized and structurally characterized by single crystal X-ray analysis. In a cation-induced color change experiment, L exhibited excellent $Hg^{2+}$ ion selectivity by showing the color change from orange-red to yellow. However, this hypochromic shift by $Hg^{2+}$ was observed for the weaker coordinating anion system such as ${NO_3}^-$ and ${ClO_4}^-$ ions. The observed anion effect is due to the strong coordination of anions inhibits the bond formation between $Hg^{2+}$ and the macrocyclic tert-N atom, which is sensitive to induce the color change. In the fluorometric experiment, L showed chelate-enhanced fluorescence change effect only with $Hg^{2+}$ ion, together with a change from yellow to green emission. The sensing ability for $Hg^{2+}$ with the proposed chemosensor L is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand).

질화규소에 의한 SiC 소결체의 제조에 관한 연구 (Febrication of $Si_3-N_4$ Bonded SiC Ceramics)

  • 정주희;김종희
    • 한국세라믹학회지
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    • 제20권1호
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    • pp.63-69
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    • 1983
  • It is know that $Si_3-N_4$ bonded SiC has almost all the valuable properties needed for the high temperature material and thus has bery wide range of applicability. Si powder and two different sized SiC powder were used as the raw mateials. Specimens were prepared by heating the green compact mode of the raw materials with polyvinyl alcohol binder in the nitrogen atmosphere. The bond-ing of SiC particles is brought about with the formation of reaction bonded silicon nitride phase between the particles he influences of the variation of the relative amounts of the raw materials and the amount of the organic binder on the density and the bend strength of the specimens were investigated. It was shown that the calculation of the amount of the nitridation of Si is somewhat complicated matter since some portion of the organic binder reacts with the Si during the firing process. Fixing the Si amount to 20w/o the distributions of the size of the SiC particles that gives the maximum density and the maximum strnegth were obtained through experiments. It was observed that the two distributions were not equal to each other. As the amount of Si increased the amount of Si reacted with nitrogen and the strength increased. The fracture mode was intergranular for the most part and the transgranular fracture was scarcely observed.

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One-Pot 합성공정으로 만든 Aluminum이 doping된 폴리카보실란으로부터 제조된 치밀한 결정화 탄화규소 섬유 (Dense Polycrystalline SiC Fiber Derived from Aluminum-doped Polycarbosilane by One-Pot Synthesis)

  • 신동근;공은배;류도형;김영희;박홍식;김현이
    • 한국세라믹학회지
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    • 제44권7호
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    • pp.393-402
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    • 2007
  • Polyaluminocarbosilane was synthesized by direct reaction of polydimethylsilane with aluminum(III)-acetylacetonate in the presence of zeolite catalyst. A fraction of higher molecular weight polycarbosilane was formed due to the binding of aluminium acetylacetonate radicals with the polycarbosilane backbone. Small amount of Si-O-Si bond was observed in the as-prepared polyaluminocarbosilane as the result. Polyaluminocarbosilane fiber was obtained through a melt spinning and was pyrolyzed and sintered into SiC fiber from $1200{\sim}2000^{\circ}C$ under a controlled atmosphere. The nucleation and growth of ${\beta}-SiC$ grains between $1400{\sim}1600^{\circ}C$ are accompanied with nano pores formation and residual carbon generation. Above $1800^{\circ}C$, SiC fiber could be sintered to give a fully crystallized ${\beta}-SiC$ with some ${\alpha}-SiC$.

A Mechanistic Study on Addition Reactions of Alicyclic Amines to 3-Butyn-2-one

  • 음익환;이정숙;육성민
    • Bulletin of the Korean Chemical Society
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    • 제19권7호
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    • pp.776-779
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    • 1998
  • Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

사용후핵연료 심지층 처분장의 완충재 소재인 WRK 벤토나이트의 pH 차이에 따른 우라늄 흡착 특성과 기작 (Uranium Adsorption Properties and Mechanisms of the WRK Bentonite at Different pH Condition as a Buffer Material in the Deep Geological Repository for the Spent Nuclear Fuel)

  • 오유나;신대현;김단우;전소영;김선옥; 이민희
    • 자원환경지질
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    • 제56권5호
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    • pp.603-618
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    • 2023
  • 사용후핵연료(Spent nuclear fuel; SNF) 심지층 처분장의 완충재 소재로서 WRK (waste repository Korea) 벤토나이트가 적합한 지를 평가하기 위하여, 대표적인 방사성 핵종인 U (uranium)에 대한 WRK 벤토나이트의 흡/탈착 특성과 흡착 기작을 규명하는 다양한 분석, 흡/탈착 실내 실험, 동역학 흡착 모델링을 다양한 pH 조건에서 수행하였다. 다양한 특성 분석 결과, 주성분은 Ca-몬모릴로나이트이며, U 흡착 능력이 뛰어난 광물학적·구조적 특징들을 가지고 있었다. WRK 벤토나이트의 U 흡착 효율 및 탈착율을 규명하기 위한 흡/탈착 실험 결과, pH 5, 6, 10, 11 조건에서 WRK 벤토나이트와 U 오염수(1 mg/L)가 낮은 비율(2 g/L)로 혼합되었음에도 불구하고 높은 U 흡착 효율(>74%)과 낮은 U 탈착율(<14%)을 보였으며, 이는 WRK 벤토나이트가 SNF 처분장에서 U 거동을 제한하는 완충재 소재로서 적절하게 사용될 수 있음을 의미한다. pH 3과 7 조건에서는 상대적으로 낮은 U 흡착 효율(<45%)이 나타났으며, 이는 U가 용액의 pH 조건에 따라 다양한 형태로 존재하며, 존재 형태에 따라 상이한 U 흡착 기작을 가지기 때문으로 판단된다. 본 연구 실험 결과와 선행연구를 바탕으로 WRK 벤토나이트의 주요 화학적 U 흡착 기작을 pH 범위에 따라 용액 내 U의 존재 형태에 근거하여 설명하였다. pH 3 이하에서 주로 UO22+ 형태로 존재하는 U는 벤토나이트 표면의 Si-O 또는 Al-O(OH)와의 정전기적 인력(예: 이온 결합)에 의해 흡착되기 때문에 pH가 감소할수록 음전하 표면이 약해지는 WRK 벤토나이트 특성에 의해 비교적 낮은 U 흡착 효율이 나타났다. pH 7 이상의 알칼리성 조건에서 U는 음이온 U-수산화 복합체(UO2(OH)3-, UO2(OH)42-, (UO2)3(OH)7- 등)로 존재하며 비교적 높은 흡착 효율이 나타내는데, 이들은 벤토나이트에 포함된 Si-O 또는 Al-O(OH)의 산소원자를 공유하거나 리간드 교환에 의해 새로운 U-복합체가 형성되어 흡착되거나 수산화물 형태의 공침(co-precipitation)에 의해 벤토나이트에 고정되기 때문이다. pH 7의 중성 조건에서는 pH 5와 6보다 오히려 낮은 U 흡착 효율(42%)이 나타났는데, 이러한 결과는 용액 내 존재하는 탄산염(carbonate)에 의해 U가 U-수산화 복합체보다 용해도가 높은 U-탄산염 복합체로 존재하는 경우 가능하다. 연구 결과 pH를 약산성 또는 염기성 조건으로 유지하거나 용액 내 존재하는 탄산염을 제한함으로써 WRK 벤토나이트의 U 흡착 효율을 높일 수 있는 것으로 나타났다.

Palladium(II) Aryloxides of Pd(2,6-(CH2NMe2)2C6H3)(OC6H4-X-p) (X = Me, NO2): Synthesis, Property and Reactivity towards Diphenyliodium Chloride

  • Jung, Hyun-Sang;Park, Yun-Sik;Seul, Jung-Min;Kim, Jong-Sook;Lee, Ho-Jin;Park, Soon-Heum
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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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.

Merrifield-Type Diaminatedpolystyrene-Cu (II) 불균일 촉매에 의한 Sarin과 Soman 분해반응 연구 (A Study on the Hydrolysis of Sarin and Soman by Merrifield-Type Diaminatedpolystyrene-Cu (II) Heterogeneous Polymers)

  • 정우영;계영식
    • 한국군사과학기술학회지
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    • 제3권1호
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    • pp.164-175
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    • 2000
  • Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

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