• Title/Summary/Keyword: Steric interaction

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Adsorption Characteristics and Structure of 4,4'-Bis(mercaptomethyl)biphenyl on Silver by Surface-enhanced Raman Scattering and Density Functional Theory Calculations

  • Eom, So Young;Lee, Yu Ran;Kim, Hong Lae;Kwon, Chan Ho
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.875-880
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    • 2014
  • Adsorption of 4,4'-bis(mercaptomethyl)biphenyl (44BMBP) on silver nanoparticles has been investigated by surface-enhanced Raman scattering (SERS) spectroscopy. In addition, the Raman spectra of 44BMBP in solid state and in basic condition have been obtained for comparative study to elicit the characteristics of adsorption. The observed Raman and SERS spectra were analyzed comparing with the normal modes and vibrational frequencies from density functional theory (DFT) calculations performed for the feasible structures of 44BMBP molecule. On the basis of excellent agreement between the calculated and the experimental results, the molecule is found to have both the cis- and trans-forms for the mercaptomethyl groups in the solid state as well as in the basic condition. In contrast, the molecule is found to be chemisorbed on the silver surface by forming two Ag-S linkages only in the cis-form but not in the trans-form due to the steric interruption, which indicates the parallel orientation of molecules on the surface. Particularly, the spectral features in the SERS spectra such as the absence of the C-H stretching band and enhancement for the out-of-plane skeletal modes are confirmatory for the parallel geometry through ${\pi}$ interaction between the phenyl rings and the metal surface, based on the electromagnetic surface selection rule.

A Preparation and Characteristics of Functional rchitecture Materials Made frm Non-metallic Minerals (비금속광물 분체의 기능성 건축소재화 특성)

  • 김병곤;최상근;박종력;전호석
    • Journal of the Korean Ceramic Society
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    • v.40 no.8
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    • pp.811-817
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    • 2003
  • Recently, application fields of non-metallic minerals by utilizing their structure properties are broadening. Especially, layered minerals have not only excellent shielding or covering ability but also absorbing and storing characteristics of chemical elements between a layers. We considered about the above mentioned characteristics and added functional substances onto their surfaces for the preparation of new environmentally friendly functional materials. In this study, natural graphite and sericite were mainly used to produce for the new environmentally friendly functional building materials. Graphite surfaces were modified with a surfactant (Alkyl Benzyle Demethyle Ammonium Chloride) for anti-bacillus and penicillium. Surface modification mechanism are that primary adsorption by differential zeta potential between graphite and ABDM and secondary adsorption by interaction between surfactant chains take place. Surfactant layers were fully formed and it was expected up to 99.7% up the efficiency of anti-bacillus and penicillium. Also the prepared functional samples have a effect to improve a various efficiency such as electromagnetic wave shield(up to 95%), deodorization(up to 80%), heat storage(5%) etc.

A Study on the Detergency Performance of Zeolite A in the Detergent Solution (세제용액 중에서 Zeolite A의 세정성능에 관한 연구)

  • Kang, Yun-Seog;Kim, Hyun-Chang;Nam, Ki-Dae
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.624-630
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    • 1997
  • Zeolite A helps an increase of detergency performance according to showing the ion exchange effect for polyvalant ions and it's detergency performance could be calculated quantitatively by using the disperse stabilization theory because it is water-insoluble material and is as colloid particles in aqueous solution. In this study, zeta potential of carbon black, cellulose, and Zeolite A were measured in each inorganic salt solutions and applied to the theory of Heterocoagulation in order to evaluate the detergency performance of Zeolite A about the particulate soil at the view point of interaction potential energy. Zeolite A was shown help an increase of detergency performance according to the increasing of the steric repulsion between Zeolite A and cellulose in $Na2CO_3$ solution and the decrease of re-deposition of carbon black on the fabric by rapid coagulation with carbon black in $Na_2SO_4$ solution.

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Quantitative Assay of Recombinant Hepatitis B Surface Antigen by Using Surface Plasmon Resonance Biosensor (Surface plasmon resonance 바이오센서를 이용한 재조합 B형 간염 표면항원의 정량분석)

  • Lee, E. K.;Ahn, S. J.;Yoo, C. H.;Ryu, K.;Jeon, J. Y.;Lee, H. I.;Choi, S. C.;Lee, Y. S.
    • KSBB Journal
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    • v.17 no.1
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    • pp.20-25
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    • 2002
  • We performed a basic experiment for rapid, on-line, real-time measurement of HBsAg by using a surface plasmon resonance biosensor to quantify the recognition and interaction of biomolecules. We immobilized the anti-HBsAg polyclonal antibody to the dextran layer on a CM5 chip surface which was pre-activated by N-hydroxysuccinimide for amine coupling. The binding of the HBsAg to the immobilized antibody was measured by the mass increase detected by the change in the SPR signal. The binding characteristics between HBsAg and its antibody followed typical monolayer adsorption isotherm. When the entire immobilized antibody was interacted, there was no additional, non-specific binding observed, which suggested the biointeraction was very specific as expected and independent of the ligand density. No significant steric hindrance was observed at 17.6 nm/$mm^2$ immobilization density. The relationship between the HBsAg concentration in the sample solution and the antigen bound to the chip surface was linear up to ca. $40\mu\textrm{g}$/mL, which is much wider than that of the ELISA method. It appeared the antigen-antibody binding was increased as the immobilized ligand density increased, but verification is warranted. This study showed the potential of this biosensor-based method as a rapid, simple, multi-sample, on-line assay. Once properly validated, it can serve as a more powerful method for HBsAg quantification replacing the current ELISA method.

Effects of PVA and CMC addition on Rheological Characteristics and Curtain Stability of GCC Based Curtain Coating Colors (PVA와 CMC 첨가가 커튼 코팅용 GCC 도공액의 유변 특성 및 커튼 안정성에 미치는 영향)

  • Choi, Eun-Heui;Kim, Chae-Hoon;Lee, Hak-Lae
    • Journal of Korea Technical Association of The Pulp and Paper Industry
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    • v.42 no.5
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    • pp.74-82
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    • 2010
  • Curtain stability without curtain contraction is critical for a successful operation in curtain coating, and this can be influenced by the change in particle dynamics and rheological properties of coating colors. In this study, polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) were added to control the rheology of GCC based curtain coating colors. Surface tension was increased slightly with increasing content of cobinder. Shear-thinning of viscosity was more pronounced for the CMC containing GCC coating colors. Complex modulus decreased when small amount of PVA was used as a cobinder, but it increased in other coating colors. Extensional viscosity was increased with increasing of the cobinder content, but CMC was more effective. Results indicate that pigment interaction with PVA is different from that with CMC. Dispersibility of coating colors was improved due to steric stabilization when small amounts of PVA was used, but flocculation occurred by bridging when the amount of PVA was increased. Dispersibility of coating colors was improved when small amount of CMC was added, while flocculation was observed by depletion effect when the concentration of CMC was increased in coating colors. Addition of cobinders at proper levels gave positive effects both in rheological properties and curtain stability. On the other hand, excessive amount of cobinders caused particle flocculation and this resulted in rheological and curtain stablity problems.

A New Functional Model of Catechol Dioxygenases: Properties and Reactivity of [Fe(BLPA)DBC]$BPh_4$

  • Lim, Ji H.;Lee, Ho J.;이강봉;Jang, Ho G.
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1166-1172
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    • 1997
  • [FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

A Study for the Effect of Solvent and Temperature on the Retention Behavior of Phenols in Reversed-Phase Liquid Chromatography (역상 액체 크로마토그래피에서 페놀류의 머무름거동에 미치는 용매와 온도의 영향에 관한 연구)

  • Lee Dai Woon;Lee Hoo Keun;Yook Keun Sung;Lee, In Ho;Cho Byung Yun
    • Journal of the Korean Chemical Society
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    • v.37 no.5
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    • pp.503-512
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    • 1993
  • The purpose of this study was to investigate the retention behavior of phenols and to predict their retention in RPLC. The retention data of twenty-five phenols were measured on a $\mu-{Bondapak}\;C_{18}$ and a polymeric $C_{18}$ columns with methanol-water and acetonitrile-water as a mobile phase. From the observation of enthalpy-entropy compensation phenomenon, the following conclusions are drawn with regard to the retention mechanism: 1) the retention mechanism of nitrophenols in different from that of metheyl-and chlorophenols in both mobile phase; 2) in methanol-water mobile phase, the retention mechanism of methyl-and chlorophenols is consistent in the range of methanol-water composition; 3) on the other hand, in the case of acetonitrile-water mobile phase, the retention mechanism depends on the volume fraction of acetonitrile. It means that the retention mechanism can not be explained only by a simple interaction. Based on retention data as compared with two columns, it may be said that the hydrophobic interaction of phenols with polymeric $C_{18}$ column was greater than that with monomeric $C_{18}$ column. The equations for predicting the retention of phenols were derived by using hydrophobic substituent constant $(\pi)$ and the sum of Hammett's constant $(\sigma)$ and Taft's steric constant $(E_s)$.

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전이금속 (Ru$^{3+}$, Ni$^{2+}$, Cu$^{2+}$, Pd$^{2+}$)-Polyaza(N$_4$) 착물의 합성과 올레핀 산화반응에 대한 촉매적 활성

  • Park, Yu Cheol;Kim, Seong Su;Na, Hun Gil;Lee, Dong Cheol;Sin, Sang Hui;Byeon, Jong Cheol
    • Journal of the Korean Chemical Society
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    • v.38 no.4
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    • pp.295-301
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    • 1994
  • The Ru(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), and Pd(Ⅱ) complexes of N$_4$-polydentate ligands(meso-Me$_6$-[14]-ane, rac-Me$_6$-[14]-ane, and cyclam) have been prepared and their catalytic activity and selectivity in the oxidation of olefins in the presence of oxidant such as NaOCl, H$_2$O$_2$, t-BuOOH, and PhIO studied. The oxidations of cyclohexene, 1-hexene, cyclooctene, 1-octene, and styrene as substrates have been investigated gas chromatographically. The Ru(Ⅲ)-N$_4$ complexes showed high selectivity for epoxide in the catalyzed oxidation of olefins with NaOCl. The catalytic activities of Ru(Ⅲ)-N$_4$ complexes were discussed in terms of the flexibility of N$_4$-polydentate ligands, the Ru(Ⅲ)-Cl bond interaction and the steric effect of oxidants. The oxidation of 1-octene using PhIO as oxidant was carried out to verify. The Pd(Ⅱ) complex turned out to be more active catalyst than the Ni(Ⅱ) complexes.

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Effect of Amine Functional Group on Removal Rate Selectivity between Copper and Tantalum-nitride Film in Chemical Mechanical Polishing

  • Cui, Hao;Hwang, Hee-Sub;Park, Jin-Hyung;Paik, Ungyu;Park, Jea-Gun
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.06a
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    • pp.546-546
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    • 2008
  • Copper (Cu) Chemical mechanical polishing (CMP) has been an essential process for Cu wifing of DRAM and NAND flash memory beyond 45nm. Copper has been employed as ideal material for interconnect and metal line due to the low resistivity and high resistant to electro-migration. Damascene process is currently used in conjunction with CMP in the fabrication of multi-level copper interconnects for advanced logic and memory devices. Cu CMP involves removal of material by the combination of chemical and mechanical action. Chemicals in slurry aid in material removal by modifying the surface film while abrasion between the particles, pad, and the modified film facilitates mechanical removal. In our research, we emphasized on the role of chemical effect of slurry on Cu CMP, especially on the effect of amine functional group on removal rate selectivity between Cu and Tantalum-nitride (TaN) film. We investigated the two different kinds of complexing agent both with amine functional group. On the one hand, Polyacrylamide as a polymer affected the stability of abrasive, viscosity of slurry and the corrosion current of copper film especially at high concentration. At higher concentration, the aggregation of abrasive particles was suppressed by the steric effect of PAM, thus showed higher fraction of small particle distribution. It also showed a fluctuation behavior of the viscosity of slurry at high shear rate due to transformation of polymer chain. Also, because of forming thick passivation layer on the surface of Cu film, the diffusion of oxidant to the Cu surface was inhibited; therefore, the corrosion current with 0.7wt% PAM was smaller than that without PAM. the polishing rate of Cu film slightly increased up to 0.3wt%, then decreased with increasing of PAM concentration. On the contrary, the polishing rate of TaN film was strongly suppressed and saturated with increasing of PAM concentration at 0.3wt%. We also studied the electrostatic interaction between abrasive particle and Cu/TaN film with different PAM concentration. On the other hand, amino-methyl-propanol (AMP) as a single molecule does not affect the stability, rheological and corrosion behavior of the slurry as the polymer PAM. The polishing behavior of TaN film and selectivity with AMP appeared the similar trend to the slurry with PAM. The polishing behavior of Cu film with AMP, however, was quite different with that of PAM. We assume this difference was originated from different compactness of surface passivation layer on the Cu film under the same concentration due to the different molecular weight of PAM and AMP.

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Optical Resolution of Free Amino Acids with Addition of Copper(II) Chelates in a Reversed-Phase Liquid Chromatography (구리(II) 킬레이트의 첨가에 의한 자유아미노산 광학이성질체의 역상 액체크로마토그래피적 분리)

  • Sun Haing Lee;Tae Sub Oh;Hong Yeup An;Kyung Sug Park;Sang Oh OH
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.879-888
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    • 1992
  • Separation of the optical isomers of free amino acids by a reversed phase high performance liquid chromatography has been studied by adding a copper(II) complex of L-proline or L-proline derivatives (hydroxy-L-proline, N-benzyl-L-proline, p-xylenyl-L-proline, p-xylenyl-hydroxy-L-proline) in the mobile phase. An OPA postcolumn detection system was used for the detection of amino acids. The chromatographic properties for the free amino acids were discussed in terms of the pH, the kinds and concentration of chelate or organic modifier. The retention behaviors of the free amino acids were considerably different from, those of DNS-amino acids or DABS-amino acids. The enantioselectivity of the free amino acids was better than that of derivatized amino acids. The enantioselectivity between the optical isomers observed by use of the Cu(II)-p-xylenyl-L-proline chiral cheleate was the best among the several copper(II) chelate. A separation mechanism could be illustrated not only by the hydrophobic interaction of the diastereomer with stationary phase but also by the steric effect of the ligand exchange reaction between the free-amino acids and copper chelate.

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