• Title/Summary/Keyword: Chemical State

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Photophysical Behaviors of Biphenylcarboxylic Acids in Various Solvents; Excited-State Geometry Change and Intramolecular Charge Transfer

  • Yoon Minjoong;Cho Dae Won;Lee Jae Young
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.613-620
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    • 1992
  • The solvent-dependent photophysical properties of 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid(4BPCA), which have a pre-twisted conformation in the ground state, have been investigated. The fluorescence spectra of 4BPCA show vibrational structure with a non-mirror image to the absorption spectra in nonpolar solvent while those of 2BPCA show no structure even in nonpolar solvents. As the solvent polarity increases, the fluorescence spectra become diffuse and broad with a strong red shift resulting in the large Stokes shift. The large fluorescence Stokes shift of BPCA's in polar solvent is also partially due to an intramolecular charge transfer (ICT) interaction in the excited state, as demonstrated by the large dipole moment in the excited state (7.6-10.6 D). The fluorescence decay behaviors of BPCA's (decay-times and their pre-exponential factors) also depend on solvent polarity in agreement with the solvent-dependent properties of the steady-state fluorecence. The data have been discussed in terms of change in the excited-state potential energy surface with respect to change of the dihedral angle of biphenyl moiety.

High-Pressure Phase Behavior of Polycaprolactone, Carbon Dioxide, and Dichloromethane Ternary Mixture Systems (Polycaprolactone, 디클로로메탄, 이산화탄소로 구성된 3성분계 고압 상거동 측정)

  • Gwon, JungMin;Shin, Hun Yong;Kim, Soo Hyun;Kim, Hwayong
    • Korean Chemical Engineering Research
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    • v.53 no.2
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    • pp.193-198
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    • 2015
  • The high-pressure phase behavior of a polycaprolactone (Mw=56,145 g/mol, polydispersity 1.2), dichloromethane, and carbon dioxide ternary system was measured using a variable-volume view cell. The experimental temperatures and pressures ranged from 313.15 K to 353.15 K and up to 300 bar as functions of the $CO_2$/dichloromethane mass ratio and temperature, at poly(D-lactic acid) weight fractions of 1.0, 2.0, and 3.0%. The correlation results were obtained from the hybrid equation of state (Peng-Robinson equation of state + SAFT equation of state) for the $CO_2$-polymer system using the van der Waals one-fluid mixing rule. The three binary interaction parameters were optimized by the simplex method algorithm.

Effect of H2O2 modification of H3PW12O40@carbon for m-xylene oxidation to isophthalic acid

  • Fang, Zhou-wen;Wen, Di;Wang, Zhi-hao;Long, Xiang-li
    • Korean Journal of Chemical Engineering
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    • v.35 no.11
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    • pp.2172-2184
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    • 2018
  • The production of isophthalic acid (IPA) from the oxidation of m-xylene (MX) by air is catalyzed by $H_3PW_{12}O_{40}$ (HPW) loaded on carbon and cobalt. We used $H_2O_2$ solution to oxidize the carbon to improve the catalytic activity of HPW@C catalyst. Experiments reveal that the best carbon sample is obtained by calcining the carbon at $700^{\circ}C$ for 4 h after being impregnated in the 3.75% $H_2O_2$ solution at $40^{\circ}C$ for 7 h. The surface characterization displays that the $H_2O_2$ modification leads to an increase in the acidic groups and a reduction in the basic groups on the carbon surface. The catalytic capability of the HPW@C catalyst depends on its surface chemical characteristics and physical property. The acidic groups play a more important part than the physical property. The MX conversion after 180 min reaction acquired by the HPW@C catalysts prepared from the activated carbon modified in the best condition is 3.81% over that obtained by the HPW@C catalysts prepared from the original carbon. The IPA produced by the former is 46.2% over that produced by the latter.

Density Measurement of Liquid Mixture and Estimation of Excess Molar Volume by A Cubic Equation of State (액체혼합물의 밀도 측정과 3차 상태방정식에 의한 과잉 몰부피의 예측)

  • Kim, Jung-Min;Bae, Hyo-Kwang
    • Korean Chemical Engineering Research
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    • v.43 no.5
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    • pp.637-640
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    • 2005
  • The density of polar-nonpolar liquid mixtures composed of methyl tert-butyl ether(MTBE) and 2,2,4-trimethylpentane, and methyl ethyl ketone (MEK) and 2,2,4-trimethylpentane, and the density of polar-polar liquid mixture of MTBE and MEK were measured by densitometer at 278.15 K, 288.15 K and 298.15 K, respectively. The excess molar volume of the binary systems calculated from the measured density was shown good agreement with the calculated one by the cubic Peng-Robinson- Stryjek-Vera (PRSV) equation of state together with Huron-Vidal mixing rule and it confirmed that the cubic PRSV equation of state could be used in the molar volume calculation of polar mixture.

Effect of metal ions on the secondary structure and activity of calf intestine phosphatase

  • Chen, Fengjuan;Liu, Guoqi;Xu, Zhihong;Zeng, Zhengzhi
    • BMB Reports
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    • v.41 no.4
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    • pp.305-309
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    • 2008
  • Cobalt is an essential microelements in many biological processes involving enzymatic activity. We found that $Zn^{2+}$ and $Mg^{2+}$, which are in the active site of native calf intestine alkaline phosphatase (CIP), can be replaced by $Co^{2+}$ directly in solution. The effect of $Co^{2+}$ concentration on the substitution reaction was examined at ratios of [$Co^{2+}$]/[CIP] from 0:1 to 8:1. The quantity of $Zn^{2+}$ in CIP decreased progressively as the ratio was increased, but the amount of $Mg^{2+}$ changed in irrregular fashion. A series of active site models of the reaction mechanism of CIP are proposed. Low pH was found to promote the replacement of $Mg^{2+}$ by $Co^{2+}$. To understand how the substitution affects the enzyme, we also solved the secondary structure of CIP after reaction with $Co^{2+}$ in different conditions.

Hierarchical porous carbon nanofibers via electrospinning

  • Raza, Aikifa;Wang, Jiaqi;Yang, Shan;Si, Yang;Ding, Bin
    • Carbon letters
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    • v.15 no.1
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    • pp.1-14
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    • 2014
  • Carbon nanofibers (CNFs) with diameters in the submicron and nanometer range exhibit high specific surface area, hierarchically porous structure, flexibility, and super strength which allow them to be used in the electrode materials of energy storage devices, and as hybrid-type filler in carbon fiber reinforced plastics and bone tissue scaffold. Unlike catalytic synthesis and other methods, electrospinning of various polymeric precursors followed by stabilization and carbonization has become a straightforward and convenient way to fabricate continuous CNFs. This paper is a comprehensive and brief review on the latest advances made in the development of electrospun CNFs with major focus on the promising applications accomplished by appropriately regulating the microstructural, mechanical, and electrical properties of as-spun CNFs. Additionally, the article describes the various strategies to make a variety of carbon CNFs for energy conversion and storage, catalysis, sensor, adsorption/separation, and biomedical applications. It is envisioned that electrospun CNFs will be the key materials of green science and technology through close collaborations with carbon fibers and carbon nanotubes.

Preparation and Characterization of Multiwalled Carbon Nanotubes/Lyocell Composite Fibers (다중벽 탄소나노튜브/리오셀 복합섬유의 제조 및 특성조사)

  • Lu, Jiang;Zhang, Huihui;Shao, Huili;Hu, Xuechao
    • Polymer(Korea)
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    • v.31 no.5
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    • pp.436-441
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    • 2007
  • In this work, the multiwalled carbon nanotubes(MWNTs) were functionalized with sodium dodecylbenzene sulfonate(SDBS) and then MWNTs/Lyocell composite fibers were prepared. The properties of MWNTs, the functionlization on the surface of MWNTs and their dispersion in the cellulose matrix were characterized by TEM, SEM, WAXD and FT-IR. The results showed that SDBS has been coated successfully onto the surface of the MWNTs by functionlization. This can improve effectively the dispersion uniformity of MWNTs in NMMO aqueous solution and is helpful to prepare a spinnable spinning dope. Moreover, the resultant MWNTs/Lyocell composite fibers still have cellulose II crystal structure, and their tensile strength and initial modulus increased with the increasing draw ratio and reached the optimal value with adding 1 wt% MWNTs. The thermal stability of the composite fiber was also improved by the addition of the MWNTs.

Phase Behavior of a PEO-PPO-PEO Triblock Copolymer in Aqueous Solutions: Two Gelation Mechanisms

  • Park, Moon-Jeong;Kookheon Char;Kim, Hong-Doo;Lee, Chang-Hee;Seong, Baek-Seok;Han, Young-Soo
    • Macromolecular Research
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    • v.10 no.6
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    • pp.325-331
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    • 2002
  • Phase behavior of a PEO-PPO-PEO (Pluronic P103) triblock copolymer in water is investigated using small-angle neutron scattering (SANS), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and rheology. Pluronic P103 shows apparent two gel states in different temperature regions. The first sol-to-gel transition at a lower temperature (i.e., the hard gel I state) turns out to be the hexagonal microphase as evidenced by the combined SANS and SAXS and the frequency dependence of both G′ and G" in rheology. In contrast to the hard gel I, the second sol-to-gel transition (i. e., the hard gel II state) at a higher temperature represents the block copolymer micelles in somewhat disordered state rather than the ordered state seen in the hard gel I. Moreover, turbidity change depending only on the temperature with four distinct regions is observed and the large aggregates with size larger than 5,000 nm are detected with DLS in the turbid solution region. Based upon the present study, two different gelation mechanisms for aqueous PEO-PPO-PEO triblock copolymer solutions are proposed.

Lyotropic Chromonic Liquid Crystals: Effects of Additives and Optical Applications

  • Park, H.S.;Tortora, L.;Vasyuta, R.M.;Golovin, A.B.;Augustin, E.;Finotello, D.;Lavrentovich, O.D.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2007.08a
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    • pp.307-310
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    • 2007
  • We describe effects of ionic and neutral additives on phase and structural behavior of the lyotropic chromonic liquid crystals used in preparation of optical elements such as polarizers and compensators.

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