• Title/Summary/Keyword: molecular adsorption

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V(IV) Species, Location and Adsorbate Interactions in VH-SAPO-42 Studied by ESR and Electron Spin-Echo Modulation Spectroscopies

  • Back, Gern-Ho;Yu, Jong-Sung;Lee, Hye-Young;Kim, Min-Sik;Lee, Yong-Ill
    • Journal of the Korean Magnetic Resonance Society
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    • v.11 no.2
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    • pp.95-109
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    • 2007
  • Vanadium-incorporated aluminophosphate microporous molecular sieve VH-SAPO-42 has been studied by electron spin resonance(ESR) and electron spin-echo modulation (ESEM) spectroscopies to determine the vanadium location and interaction with various adsorbate molecules. The results are interpreted in terms of V(IV) ion location and coordination geometry. Assynthesized VH-SAPO-42 contains only vanadyl species with distorted octahedral or trigonal bipyramidal coordination. Vanadium incorporated into H-SAPO-42 occupied extra-framework site. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is identified as a $VO(H_2O)_2^{2+}$ complex coordinated to three framework oxygen atoms bonded to aluminum. When hydrated VH-SAPO-42 is dehydrated at elevated temperature by calcination, species A loses its water ligand and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$ at high temperature, thus suggesting oxidation of $V^{4+}$ to $V^{5+}$. When dehydrated VH-SAPO-42 makes contact with $D_2O$ at room temperature, the ESR signal of species A is regained. The species is assumed as a $VO(O_f)_3(D_2O)_2$ by considering three framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-42 results in another new vanadium species D, which is identified as a $VO(CD_3OH)_2$ complex. When deuterated ethylene is adsorbed on dehydrated VH-SAPO-42, another new vanadium species E identified as a $VO(C_2D_4)^{2+}$, is observed. Possible coordination geometries of these various complexes are discussed.

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Hydrogen Separation of Carbon Molecular Sieve Membranes Derived from Polyimides Having Decomposable Side Groups (열분해성 그룹이 도입된 폴리이미드로부터 유도된 탄소분자체막의 수소 분리 특성)

  • Young Moo Lee;Youn Kook Kim;Ji Min Lee;Ho Bum Park
    • Membrane Journal
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    • v.14 no.2
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    • pp.99-107
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    • 2004
  • Carbon molecular sieve (CMS) membranes were prepared by pyrolysis of polyimides having carboxylic acid groups and applied to the hydrogen separation. The polymeric membranes having carboxylic acid groups showed different steric properties as compared with polymeric membranes having other side groups ($-CH_3$ and $-CF_3$) because of the hydrogen bond between the carboxylic acid groups. However, the microporous CMS membranes were significantly affected by the decomposable side groups evidenced from the wide angle X-rat diffraction, nitrogen adsorption isotherms, and single gas permeation measurement. Furthermore, the gas separation properties of the CMS membranes were essentially affected by the pyrolysis temperature. As a result, the CMS membranes Prepared by Pyrolysis of polyimide containing carboxylic acid froups at $700^{\circ}C$ showed the $H_2$ permeability of 3,809 Baller [$1{\times}10^{-10}$ H $\textrm{cm}^$(STP)cm/$\textrm{cm}^2$.s.cmHg], $H_2$/$N_2$, selectivity of 46 and $H_2$/$CH_4$ selectivity of 130 while the CMS membranes derived from polyimide showed the H$_2$ permeability of 3,272 Barrer, $H_2$/$N_2$ selectivity of 136 and $H_2$/$CH_4$ selectivity of 177.

Comparative Study of the Standard Plaque Assay with Solid-overlay and Immunofocus Assay for Varicella-zoster Virus Titration (수두바이러스의 정량에 있어서 Solid-overlay Standard Plaque Assay와 Immunofocus Assay의 효용성 비교 연구)

  • Lee, Hwa-Kyung;Jeong, Yong-Seok
    • The Journal of Korean Society of Virology
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    • v.30 no.1
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    • pp.61-70
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    • 2000
  • Standard plaque assay using agarose-overlay has long been used for titration of many infectious virus particle. Plaque assay for the titration of varicella-zoster virus and its live vaccine requires three intermittent agarose overlay to visualize plaques. Overall procedure of the assay takes at least nine days from virus inoculation and microbe contamination including fungi is frequently accompanied during incubation period. We studied whether an immunofocus assay in conjunction with peroxidase-mediated immunohistochemical reaction may replace the standard plaque assay for the virus titration by comparing the two methods. A linear relationship was observed between number of foci and virus dilution. The number of foci in a given dilution of virus appeared a little higher than counted plaques formed in standard plaque assay. Independent titration results obtained from two assay methods for a given dilution of virus demonstrated a strong correlation ($r^2=0.99$). Foci of virus infected cells as revealed by the enzyme reaction could be counted either 4 days post-infection (p.i.) under low magnification (40X) microscopy, or 6 days p.i. by naked eye observation. Larger size of cell cuture plate, virus adsorption at $35^{\circ}C$, and 10% FBS in diluent appeared to be better conditions for the assay. Immunofocus assay will be an effective and dependable titration method for varicella-zoster virus and its live vaccine in place of the standard plaque assay in respect to accuracy, costs, and experimental convenience.

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Synthetic Characteristics of AlPO$_4$-5 Molecular Sieve (AlPO$_4$-5 분자체의 합성 특성)

  • Sung Hwa Jhung;Suk Bong Hong;Young Sun Uh;Hakze Chon
    • Journal of the Korean Chemical Society
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    • v.37 no.10
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    • pp.867-873
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    • 1993
  • Influences of crystallization time and $H_2O/Al_2O_3$ ratio of the reaction mixtures on the synthesis of AlPO$_4$-5 molecular sieve have been studied by X-ray powder diffraction, nitrogen adsorption, scanning electron microscope (SEM), and solid state $^{27}$Al magic angle spinning nuclear magnetic resonance (MAS NMR) techniques. The degree of crystallinity of AlPO$_4$-5 follows a sigmoid pattem as crystallization time increases. The induction period is shorter than 1 h when the crystallization process is carried out at 150$^{\circ}$C. The conversion of reactants to product, AlPO$_4$-5, can be clearly observed, and all of the determined physical properties change abruptly after about 2 h. It is found that increase in $H_2O/Al_2O_3$ ratio of the reaction mixtures not only changes the crystal morphology from aggregates to hexagonal single crystals, but also results in the formation of longer AlPO$_4$-5 crystals.

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Single-Protein Molecular Interactions on Polymer-Modified Glass Substrates for Nanoarray Chip Application Using Dual-Color TIRFM

  • Kim, Dae-Kwang;Lee, Hee-Gu;Jung, Hyung-Il;Kang, Seong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.28 no.5
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    • pp.783-790
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    • 2007
  • The immobilization of proteins and their molecular interactions on various polymer-modified glass substrates [i.e. 3-aminopropyltriethoxysilane (APTS), 3-glycidoxypropyltrimethoxysilane (GPTS), poly (ethylene glycol) diacrylate (PEG-DA), chitosan (CHI), glutaraldehyde (GA), 3-(trichlorosilyl)propyl methacrylate (TPM), 3'-mercaptopropyltrimethoxysilane (MPTMS), glycidyl methacrylate (GMA) and poly-l-lysine (PL).] for potential applications in a nanoarray protein chip at the single-molecule level was evaluated using prismtype dual-color total internal reflection fluorescence microscopy (dual-color TIRFM). A dual-color TIRF microscope, which contained two individual laser beams and a single high-sensitivity camera, was used for the rapid and simultaneous dual-color detection of the interactions and colocalization of different proteins labeled with different fluorescent dyes such as Alexa Fluor® 488, Qdot® 525 and Alexa Fluor® 633. Most of the polymer-modified glass substrates showed good stability and a relative high signal-to-noise (S/N) ratio over a 40-day period after making the substrates. The GPTS/CHI/GA-modified glass substrate showed a 13.5-56.3% higher relative S/N ratio than the other substrates. 1% Top-Block in 10 mM phosphate buffered saline (pH 7.4) showed a 99.2% increase in the blocking effect of non-specific adsorption. These results show that dual-color TIRFM is a powerful methodology for detecting proteins at the single-molecule level with potential applications in nanoarray chips or nano-biosensors.

Mechanism of Lubricity Improvement by Biodiesels (바이오디젤 윤활성 향상 메커니즘)

  • Lim, Young-Kwan;Lee, Jae-Min;Kim, Jong-Ryeol;Ha, Jong-Han
    • Tribology and Lubricants
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    • v.32 no.3
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    • pp.95-100
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    • 2016
  • As an alternative fuel, biodiesel has excellent lubricating property. Previously, our research group reported that the properties of biodiesels depended on their composed molecular structure. In this study, we investigate lubricity and the mechanism of lubricity improvement of synthesized biodiesel molecules. We synthesize four types of biodiesel components from fatty acid via fisher esterification and soybean biodiesel from soybean oil via transesterification in high yield (92-96%). We analyze the lubricity of the five 5 types of biodiesel using HFRR (high frequency reciprocating rig). We estimate that the mechanism of lubricity is relevant to the molecular structure and structure conversion of biodiesel. The test results indicate that the longer the length of molecules and the higher the content of olefin, the better the lubricity of the biodiesel molecules. However, the wear scar size of the first test samples’ do not show a regular pattern with the wear scar size of the second test samples’. Moreover, we investigated the structure conversion of the biodiesels by using GC-MS for the recovered biodiesel samples from the HFRR test. However, we do not detect structure conversion. Thus, we conclude that the lubricity of biodiesel depends on how effectively solid adsorption and boundary lubrication occurs based on the size of the molecule and the content of olefin in the molecule. In addition, HFRR test condition in not sufficient for Diels-Alder cyclization of biodiesel components.

The Study on Location and Adsorbate Interaction for Vanadium Species in $VO^{2+}-SAPO-5$ by Electron Spin Resonance and Electron Spin Echo Modulation Spectroscopies

  • Back Gern-Ho;Park Sung-Gun;Lee Chul-Wee
    • Journal of the Korean Magnetic Resonance Society
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    • v.9 no.2
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    • pp.138-154
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    • 2005
  • Vanadium-incorporated aluminophosphate molecular sieve $VO^{2+}-SAPO-5$ was studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium structure and interaction with various adsorbate molecules. It was found that the main species at low concentration of vanadium is a monomeric vanadium units in square pyramidal or distorted octahedral coordination, both in oxidation state (IV) for the calcined hydrated material and in oxidation state (V) for the calcined material. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. It is suggested as a $VO(H_2O)_3^{2+}$ complex coordinated to two framework oxygen bonded aluminum. When calcined, hydrated $VO^{2+}-}SAPO-5$ is dehydrated at elevated temperature, a species loses its water ligands and transforms to $VO^{2+}$ ions coordinated to two framework oxygens (species B). Species B reduces its intensity, significantly after treatment with $O_2\;at\;600^{\circ}C$ for 5 h, thus suggesting oxidation of $V^{4+}\;to\;V^{5+}$. When dehydrated $VO^{2+}-SAPO-5$ contacts with $D_2O$ at room temperature, the EPR signal of species A is observed. Thus species assumed as a $VO^{2+}(O_f)_2(D_2O)_3$, by considering two framework oxygens. Adsorption of deuterated ethanol, propanol on dehydrated $VO^{2+}_{-}SAPO-5$ result in another new vanadium species E and F, respectively, which are identified as a $VO^{2+}-(CH_3CH_2OD)_3,\;VO^{2+}-(CH_3CH_2CH_2OD)_2$ complex. When deuterated benzene is adsorbed on dehydrated $VO^{2+}-SAPO-5$, another new vanadium species G, identified as a $VO^{2+}-(C_6D_6)$ is observed. Possible coordination geometries of these various complexes are discussed.

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Adherence of Salivary Proteins to Various Orthodontic Brackets (다양한 교정용 브라켓 표면에 부착하는 타액단백질에 관한 연구)

  • Ahn, Sug-Joon;Ihm, Jong-An;Nahm, Dong-Seok
    • The korean journal of orthodontics
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    • v.32 no.6 s.95
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    • pp.443-453
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    • 2002
  • The principal aims of this study were to identify the composition of salivary pellicles formed on various orthodontic brackets and to obtain a detailed information about the protein adsorption profiles from whole saliva and two major glandular salivas. Four different types of orthodontic brackets were used. All were upper bicuspid brackets with a $022{\times}028$ slot Roth prescription; stainless steel metal, monocrystalline sapphire, polycrystalline alumina, and plastic brackets. Bracket pelicles were formed by the incubation of orthodontic brackets with whole saliva, submandibular-sublingual saliva, and parotid saliva for 2 hours. The bracket pellicles were extracted and confirmed by employing sodium dodecyl sulfatepolyacrylamide gel electrophoresis, Western transfer methods, and immunodetection. The results showed that low-molecular weight salivary mucin, ${\alpha}-amylase$, secretory IgA (sIgA), acidic proline-rich proteins, and cystatins were attached to all of these brackets regardless of the bracket types. High-molecular weight mucin, which promotes the adhesion of Streptococcus mutans, did not adhere to uy orthodontic brackets. Though the same components were detected in all bracket pellicles, however, the gel profiles showed qualitatively and quantitatively different pellicles, according to the origins of saliva and the bracket types. In particular, the binding of sIgA was more prominent in the pellicles from parotid saliva and the binding of cystatins was prominent in the pellicles from the form plastic brackets. This study indicates that numerous salivary proteins adhere to the orthodontic brackets and these salivary proteins adhere selectively according to bracket types and the types of the saliva.

Theoretical Study on Interactions between N-Butylpyridinium Nitrate and Thiophenic Compounds

  • Lu, Renqing;Liu, Dong;Wang, Shutao;Lu, Yukun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.6
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    • pp.1814-1822
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    • 2013
  • By using density functional theory calculations, we have performed a systemic study on the electronic structures and topological properties of interactions between N-butylpyridinium nitrate ($[BPY]^+[NO_3]^-$) and thiophene (TS), benzothiophene (BT), dibenzothiophene (DBT), naphthalene (NAP). The most stable structure of $[BPY]^+[NO_3]^-$ ion pair indicates that hydrogen bonding interactions between oxygen atoms on $[NO_3]^-$ anion and C2-H2 on pyridinium ring play a dominating role in the formation of ion pair. The occurrence of hydrogen bonding, ${\pi}{\cdots}$H-C, and ${\pi}{\cdots}{\pi}$ interactions between $[BPY]^+[NO_3]^-$ and TS, BT, DBT, NAP has been corroborated at the molecular level. But hydrogen bonding and ${\pi}{\cdots}{\pi}$ interactions between $[BPY]^+[NO_3]^-$ and NAP are weak in terms of structural properties and NBO, AIM analyses. DBT is prior to adsorption on N-butylpyridinium nitrate ionic liquid.