• 제목/요약/키워드: Molecular Spectroscopy

검색결과 827건 처리시간 0.024초

Evidence of Molecular Rearrangement in Benzyl-type Radicals

  • Yoon, Young-Wook;Lee, Seung-Woon;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
    • /
    • 제31권10호
    • /
    • pp.2783-2785
    • /
    • 2010
  • Searching for new molecular radicals which are believed to play an important role as reaction intermediates in aromatic chain reactions, we have applied the technique of corona excited supersonic expansion employing a pinhole-type glass nozzle to obtain the vibronic spectrum from the corona discharge of precursor 3,5-difluorotoluene with a large amount of inert carrier gas helium. An analysis of the observed spectrum revealed that many vibronic bands are from other isomeric difluorobenzyl radicals generated in the jet by migration of the fluorine atom or methylene group to the adjacent position in the 3,5-difluorobenzyl radical. A possible mechanism was proposed for the formation of other isomers by using a bridged cyclic intermediate structure.

Molecular Bonding Force and Stiffness in Amine-Linked Single-Molecule Junctions Formed with Silver Electrodes

  • Kim, Taekyeong
    • 대한화학회지
    • /
    • 제59권2호
    • /
    • pp.132-135
    • /
    • 2015
  • Bonding force and stiffness in amine-linked single-molecule junctions for Ag electrodes were measured using a home-built conducting atomic force microscope under ambient conditions at room temperature. For comparison, Au electrodes were used to measure the rupture force and stiffness of the molecular junctions. The traces of the force along with the conductance showed a characteristic saw-tooth pattern owing to the breaking of the metal atomic contacts or the metal-molecule- metal junctions. We found the rupture force and stiffness for Ag are smaller than those for Au electrodes. Furthermore, we observed that the force required to break the amine-Ag bond in the conjugated molecule, 1,4-benzenediamine, is smaller than in 1,4-butanediamine which is fully saturated. These results consist with the previous theoretical calculations for the binding energies of the nitrogen bonded to Ag or Au atoms.

Photoacoustic Spectroscopic Study on Cobalt Incorporation onto the Surface of Mesoporous Molecular Sieves

  • 박동호;박성수;최상준
    • Bulletin of the Korean Chemical Society
    • /
    • 제20권6호
    • /
    • pp.715-719
    • /
    • 1999
  • The incorporation of cobalt into mesoporous molecular sieves MCM-41 and MCM-48 was carried out. Co-PO/MCM41 and Co-PO/MCM48 were prepared using Co(II) acetate solution adjusted to pH = 3.0 with phosphoric acid by the incipient wetness method. Photoacoustic spectroscopy (PAS) was used to study the local environments of Co(II) incorporated into mesopores. The band around 500 nm in PAS of as-prepared Co-PO/MCM41 and Co-PO/MCM48 with Co(II) acetate solution was changed to triplet bands around 600 nm. This could be assigned to the 4 A2(F)-> 4T1(P) transition of Co(II) surrounded tetrahedrally by oxygen ions after calcination. It may be attributable to that the octahedral cobalt species containing phosphate ligands in coordination sphere reacting with framework's silanol groups to be dispersed atomically onto the surface of mesoporous molecular sieves as a tetrahedral species. This is unlike that the Co in Co-Cl/MCM41 and direct-synthesized Co-MCM41 transforms to Co oxide phase upon calcination. Co-PO/MCM41 and Co-PO/MCM48 were stable while treated with water.

이중블록공중합체 역마이셀 주형을 이용한 Au@Ag 코어-쉘 나노입자 2차원 패턴 제어 및 표면 플라즈몬 기반 광학적 특성 연구 (Controll over the Au@Ag Core-shell Nanoparticle 2D Patterns via Diblock Copolymer Inverse Micelle Templates and Investigation of the Surface Plasmon Based Optical Property)

  • 윤민지;김지현;장윤희;이지은;정경화;전리나;김동하
    • 대한화학회지
    • /
    • 제57권5호
    • /
    • pp.618-624
    • /
    • 2013
  • 코어-쉘 형태의 금@은 나노입자가 재구성된 자기조립 블록공중합체 역마이셀 박막에 선택적으로 결합하여 특정 클러스터 배열을 형성하도록 유도하였고, 생성된 배열에 대하여 나노입자 사이의 상호작용에 따른 국소 표면 플라즈몬 결합 현상을 고찰하였다. 금@은 나노입자 배열을 제조하기 위해 폴리스티렌-블록-폴리(4-비닐피리딘) 역마이셀 박막을 주형으로 선택하였으며, 특정 용매 처리에 의해 선택적으로 유도되는 역마이셀 박막의 재구성 현상을 바탕으로, 폴리비닐피롤리돈으로 안정화된 금@은 나노입자의 도입 방법에 따라 규칙적이거나 무질서한 두가지 유형의 금@은 나노입자의 배열을 제조하였다. 금@은 나노입자를 안정화시키기 위하여 사용한 리간드 종류, 금 코어와 은 쉘의 결합, 은 쉘의 두께 변화, 및 금@은 나노입자의 배열 형태 등의 다양한 변수에 따라 발현되는 국소 표면 플라즈몬 결합 현상을 자외선-가시광 흡광 스펙트럼으로 관찰하였다. 최종적으로 나노입자 배열을 표면 증강 라만 산란 현상을 고찰하기 위한 기판으로써 응용하였으며 금@은 나노입자 패턴의 결합 정도에 상응하는 현저히 증강된 라만 신호를 관찰하였다.

High Level of Soluble Expression in Escherichia coli and Characterisation of the Cloned Bacillus thuringiensis Cry4Ba Domain III Fragment

  • Chayaratanasin, Poramed;Moonsom, Seangdeun;Sakdee, Somsri;Chaisri, Urai;Katzenmeier, Gerd;Angsuthanasombat, Chanan
    • BMB Reports
    • /
    • 제40권1호
    • /
    • pp.58-64
    • /
    • 2007
  • Similar to the other known structures of Bacillus thuringiensis Cry $\delta$-endotoxins, the crystal structure of the 65-kDa activated Cry4Ba toxin comprises three domains which are, from the N- to C-terminus, a bundle of $\alpha$-helices, a three-$\beta$-sheet domain, and a $\beta$-sandwich. To investigate the properties of the C-terminal domain III in isolation from the rest of the toxin, the cloned Cry4Ba-domain III was over-expressed as a 21-kDa soluble protein in Escherichia coli, which cross-reacted with anti-Cry4Ba domain III monoclonal antibody. A highly-purified domain III was obtained in a monomeric form by ion-exchange and size-exclusion FPLC. Circular dichroism spectroscopy indicated that the isolated domain III fragment distinctly exists as a $\beta$-sheet structure, corresponding to the domain III structure embodied in the Cry4Ba crystal structure. In vitro binding analysis via immuno-histochemical assay revealed that the Cry4Ba-domain III protein was able to bind to the apical microvilli of the susceptible Stegomyia aegypti larval midguts, albeit at lower-binding activity when compared with the full-length active toxin. These results demonstrate for the first time that the C-terminal domain III of the Cry4Ba mosquito-larvicidal protein, which can be isolated as a native folded monomer, conceivably participates in toxin-receptor recognition.

Interaction between IGFBP-5 and TNFR1

  • Kim, Eun-Jung;Jeong, Mi-Suk;Hwang, Jae-Ryoung;Lee, Je-Ho;Jang, Se-Bok
    • Bulletin of the Korean Chemical Society
    • /
    • 제31권7호
    • /
    • pp.2019-2024
    • /
    • 2010
  • Insulin-like growth factor binding protein 5 (IGFBP-5) plays an important role in controlling cell survival, differentiation and apoptosis. Apoptosis can be induced by an extrinsic pathway involving the ligand-mediated activation of death receptors such as tumor necrosis factor receptor 1 (TNFR1). To determine whether IGFBP-5 and TNFR1 interact as members of the same apoptosis pathway, recombinant IGFBP-5 and TNFR1 were isolated. The expression and purification of the full-length TNFR1 and truncated IGFBP-5 proteins were successfully performed in E. coli. The binding of both IGFBP-5 and TNFR1 proteins was detected by surface plasmon resonance spectroscopy (BIAcore), fluorescence measurement, electron microscopy, and size-exclusion column (SEC) chromatography. IGFBP-5 indeed binds to TNFR1 with an apparent $K_D$ of 9 nM. After measuring the fluorescence emission spectra of purified IGFBP-5 and TNFR1, it was found that the tight interaction of these proteins is accompanied by significant conformational changes of one or both. These results indicate that IGFBP-5 acts potently as a novel ligand for TNFR1.

Biochemical characterization of the lipid-binding properties of a broccoli cuticular wax-associated protein, WAX9D, and its application

  • Ahn, Sun-Young;Kim, Jong-Min;Pyee, Jae-Ho;Park, Heon-Yong
    • BMB Reports
    • /
    • 제42권6호
    • /
    • pp.367-372
    • /
    • 2009
  • In this study, we showed that WAX9D, a nonspecific lipid-transfer protein found in broccoli, binds palmitate (C16) and stearate (C18) with dissociation constants of 0.56 ${\mu}M$ and 0.52 ${\mu}M$, respectively. WAX9D was fused to thioredoxin protein by genetic manipulation to enhance its solubility. The data revealed strong interaction of Trx-WAX9D with palmitate and stearate. The dissociation constants of Trx-WAX9D for palmitate and stearate were 1.1 ${\mu}M$ and 6.4 ${\mu}M$, respectively. The calculated number of binding sites for palmitate and stearate was 2.5 to 2.7, indicating that Trx-WAX9D can bind three molecules of fatty acids. Additionally, Trx-WAX9D was shown to inhibit the apoptotic effect of palmitate in endothelial cells. Our data using Trx-WAX9D provide insight into the broad spectrum of its biological applications with specific palmitate binding.

Analytical Application of Glow Discharge Atomic Absorption Spectroscopy (GD-AAS) Using Three Types of Jet Configurations Under Power Mode

  • Hwang, Jun Ho;Lee, Ki Beom;Kim, Min Su;Lee, Seong Ro;Kim, Hasuck;Kim, Hyo Jin;Lee, Gae Ho
    • 분석과학
    • /
    • 제8권4호
    • /
    • pp.443-448
    • /
    • 1995
  • Three anode configurations of six-jet, cone-jet and cylindrical-jet are tested for their analytical performance under power mode operation. The effect of pressure, power and gas flow rate on atomic absorption signals have been studied. The increase of atomic absorption signal of sample element is observed at a fixed pressure in all configurations as the gas flow rate increase up to 300-600 seem, and as the power dissipated in the glow discharge cell increase. The lower the pressure is in the glow discharge cell at a fixed discharge power and argon flow rate, the greater the absorbance of sample element is. The optimum conditions are taken from these data and a calibration curve of Cu in low-alloy steel sample is obtained. In this calibration curve, six-jet configuration shows the best analytical results varies as the sample element.

  • PDF

Influence of Quaternization on UCST Properties of Hydroxyl-Derivatized Polymers

  • Lee, Hyung-Il
    • Bulletin of the Korean Chemical Society
    • /
    • 제35권10호
    • /
    • pp.3001-3004
    • /
    • 2014
  • A series of hydroxyl-derivatized quaternized polymers were successfully synthesized by atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed 1,3-dipolar cycloaddition of azide and alkynes (click chemistry), followed by quaternization reactions. ATRP was employed to synthesize poly(2-hydroxyethyl methacrylate) (PHEMA), followed by introduction of alkyne groups using pentynoic acid, leading to HEMA-Alkyne. 2-Azido-1-ethanol and 3-azido-1-propanol were combined with the HEMA-Alkyne backbone via click reaction, resulting in triazole-ring containing hydroxyl-derivatized polymers. Quaternization reactions with methyl iodide were conducted on the triazole ring of each polymer. Molecular weight, molecular weight distribution, and the degree of quaternization (DQ) were determined by gel permeation chromatography (GPC) and $^1H$ NMR spectroscopy. The average molecular weight ($M_n$) of the resulting polymers ranged from $5.9{\times}10^4$ to $1.05{\times}10^5g/mol$ depending on the molecular architecture. The molecular weight distribution was low ($M_w/M_n$ = 1.26-1.38). The transmission spectra of the 0.1 wt % aqueous solutions of the resulting quaternized polymers at 650 nm were measured as a function of temperature. Results showed that the upper critical solution temperature (UCST) could be finely controlled by the level of DQ.

Resolution of a Multi-Step Electron Transfer Reaction by Time Resolved Impedance Measurements: Sulfur Reduction in Nonaqueous Media

  • Park, Jin-Bum;Chang, Byoung-Yong;Yoo, Jung-Suk;Hong, Sung-Young;Park, Su-Moon
    • Bulletin of the Korean Chemical Society
    • /
    • 제28권9호
    • /
    • pp.1523-1530
    • /
    • 2007
  • The first reduction peak of the cyclic voltammogram (CV) for sulfur reduction in dimethyl sulfoxide has been studied using time resolved Fourier transform electrochemical impedance spectroscopic (FTEIS) analysis of small potential step chronoamperometric currents. The FTEIS analysis results reveal that the impedance signals obtained during short potential steps can be resolved into electron transfer reactions of two different time constants in a high frequency region. The FTEIS method provides snap shots of impedance profiles during an earlier phase of the reaction, leading to time resolved EIS measurements. Our results obtained by the FTEIS analysis are consistent with a series of electron transfer and chemical equilibrium steps of a complex reaction, making up an ECE (electrochemical-chemical-electrochemical) mechanism postulated from the results of computer simulation.