• Title/Summary/Keyword: Protic

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Dissociation Constants of Dibasic Carboxylic Acids in Methanol, N, N-Dimethylformamide and Acetonitrile (메탄올, N, N-Dimethylformamide 및 Acetonitrile 속에서 2염기성 카르복시산의 해리상수)

  • Moon Su-Chan
    • Journal of the Korean Chemical Society
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    • v.16 no.6
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    • pp.369-372
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    • 1972
  • The dissociation constants of dibasic carboxylic acids $(HOOC(CH_2)_nCOOH$, n = 0~4] in methanol, N, N-dimethylformamide and acetonitrile have been determined by the potentiometric method with a glass electrode. The difference between over-all dissociation constants in each other solvent is found to be of the same order of magnitude, and the $K_1/K_2$ ratios in aprotic dimethylformamide and acetonitrile are much greater than those in protic methanol and water.

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Solvent Effect in Nucleophilic Reactions of Substituted Benzoyl Chlorides with p-Nitroaniline (치환염 벤조일과 파라니트로아닐린과의 친핵반응에 미치는 용매효과에 관한 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.251-258
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    • 1974
  • The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

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Intramolecular Hydrogen Bonding Effect on the Excited-State Intramolecular Charge Transfer of p-Aminosalicylic Acid

  • 김양희;윤민중
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.980-985
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    • 1998
  • The excited-state intramolecular proton transfer (ESIPT) emission has been observed for 0.01 mM p-aminosalicylic acid (AS) in nonpolar aprotic solvents as demonstrated by the large Stokes' shifted fluorescence emission around 440 nm in addition to the normal emission at 330 nm. However in aprotic polar solvent such as acetonitrile, the large Stokes' shifted emission band becomes broadened, indicating existence of another emission band originated from intramolecular charge transfer (ICT). It is noteworthy that in protic solvents such as methanol and ethanol the normal and ICT emissions are quenched as the AS concentration decreases, followed by the appearance of new emission at 380 nm. These results are interpreted in terms of ESIPT coupled charge transfer in AS. Being consistent with these steady-state spectroscopic results, the picosecond time-resolved fluorescence study unravelled the decay dynamics of the ESIPT and ICT state ca. 300 ps and ca. 150 ps, respectively with ca. 40 ps for the relaxation time to form the ICT state.

Photocyclization of α-(o-Ethylphenyl)acetophenone in Zeolites

  • 노태희;최경인;권혁순;장동조;박봉서
    • Bulletin of the Korean Chemical Society
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    • v.20 no.5
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    • pp.539-542
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    • 1999
  • The diastereoselectivity in the photocyclization of α-(o-ethylphenyl)acetophenone(1) to 1-methyl-2-phenyl-2-indanol was studied in zeolites X and Y, and compared with that in isotropic solvents. The yields of E-diastereomer at the irradiation of 1 in protic solvents were higher than those in aprotic solvents. The ratios of E-diastereomer to Z-diastereomer in zeolites X and Y were much higher than those in isotropic solvents. The E/Z ratios at the irradiation of 1 in zeolites X were also found to be dependent on the cations present. As the cation size increased from Li+ to Cs+, the ratio decreased. However, any pattern in the E/Z ratios was not found in zeolites Y. The diastereoselectivity observed in the zeolites was interpreted by the conformational restriction imposed by the cavity size. An efficient oxidation of 1 in zeolites RbX and CsX was also observed.

Electrochemical Properties of Trimethylammonium Tetrafluoroborate in Electrochemical Double-Layer Capacitors

  • Lee, Sooyeon;Lee, Kyung Min;Kim, Ketack
    • Journal of Electrochemical Science and Technology
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    • v.13 no.2
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    • pp.254-260
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    • 2022
  • Trimethylammonium tetrafluoroborate (TriMA BF4), consisting of the smallest trialkylammonium ion, was investigated for use in electrochemical double-layer capacitors. Despite the presence of a proton in TriMA+, cycle life tests in acetonitrile (AN) and -butyrolactone (GBL) showed a good capacity retention with a 1.8 V cut-off voltage. The rate of electrolysis of TriMA BF4 in GBL was lower than that in AN because of the lower conductivity in GBL. As a consequence, the cells based on GBL achieved a higher capacitance and longer life than those with AN. TriMA BF4 had a higher conductivity and lower viscosity than the quaternary salt tetraethylammonium tetrafluoroborate in GBL, as well as higher ionic mobility, these factors resulted in a higher rate capability.

Halogen Exchange Reactions of Benzyl Halides Part Ⅲ-Kinetics of Reactions of Bromide and Iodide Ions with Benzyl Chloride and Bromide in Absolute Acetone (벤질 할라이드의 할로겐 교환반응 (제Ⅲ보) 아세톤 중에서의 염화 및 브롬화 벤질과 브롬화 및 요오드화 이온간의 교환반응)

  • Hangbo Myung-Hwan;Lee Bon-su;Lee Ik Choon
    • Journal of the Korean Chemical Society
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    • v.13 no.2
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    • pp.109-114
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    • 1969
  • Halogen exchange reactions of benzyl halides have been studied in absolute acetone. Rate constants were calculated using an integrated rate expression derived for the reaction involving ion-pair association. The order of nucleophilicity of halide ions in acetone was found to be a reverse of the order in 90% aqueous enthanol solvent. This was interpreted by means of HSAB principle and solvation of halide ions. Net increase in rate of reaction in acetone compared with the rate in protic solvent resulted from large increase in ${\Delta}S^\neq$ rather than decrease in ${\Delta}H^\neq$. The solvation of the transition state also contribute to the net increase in rate.

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Solvent Treatment for PEDOT:PSS Conductivity Enhancement

  • Hwang, Gi-Hwan;Jeong, Won-Seok;Nam, Sang-Hun;Yu, Jeong-Hun;Ju, Dong-Hun;Bu, Jin-Hyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.333-333
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    • 2013
  • The poor conductivity of poly (3,4-ethylene dioxythiophene): poly (styrenesulfonate) (PEDOT:PSS) film hinders to use for a flexible electrode in solar cells. In this report we demonstrate that the conductivity of PEDOT:PSS film can be enhanced by modifying structures in a mixture of PEDOT: PSS aqueous solution and various organic solvents such as polar protic (2-propanol, methanol, ethanol, formic acid) and aprotic solvents (acetone and acetonitrile). To comparatively study the structural effects on the resulted electrical properties, the films are spin-coated on glasses and ITO. At the same time, a contact angle goniometer is used for clarifying a mechanism of wettability of PEDOT (hydrophobic) and PSS (hydrophilic) on the observed conductivity. The structures and electrical properties are investigated by FE-SEM (Field Emission Scanning Electron Microscopy), AFM (Atomic Force Microscopy), and 4-point probe, respectively.

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Morphology and swelling property of chitosan microapsules and microbeads prepared by W/O emulsion (W/O 에멀젼에 의한 chitosan microcapsule 및 microbead의 morphology와 팽윤성)

  • 하병조;이옥섭
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.21 no.2
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    • pp.49-56
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    • 1995
  • Chitosan microcapsules and microbeads were prepared by W/O emulsion method, and their morphologies were observed through SEM. The microcapsules have skin layer of 8 Um and 250 Um of mean diameter, The swelling test showed higher s welling ability in protic solvents than in aphotic solvents. After containing moth-yl violet in the microcapsules, the release patterns were investigated. The results sho wed that the addition of Iysozyme in pH 5.1 acetate buffer accelerated the re-lease rate. In case of the microbeads, the mean diameter was about 70 Um. The surface of the microbeads showed porous structures. The swelling ability of the beads revealed two times higher than the one of the microcapsules.

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The Influence of Mixed Solvents Volatility on Charge State Distribution of Peptides During Positive Electrospray Ionization Mass Spectrometry

  • Nielsen, Birthe V.;Abaye, Daniel A.;Nguyen, Minh T.L.
    • Mass Spectrometry Letters
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    • v.8 no.2
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    • pp.29-33
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    • 2017
  • Understanding the mechanisms that control and concentrate the observed electrospray ionisation (ESI) response from peptides is important. Controlling these mechanisms can improve signal-to-noise ratio in the mass spectrum, and enhances the generation of intact ions, and thus, improves the detection of peptides when analysing mixtures. The effects of different mixtures of aqueous: organic solvents (25, 50, 75%; v/v): formic acid solution (at pH 3.26) compositions on the ESI response and charge-state distribution (CSD) during mass spectrometry (MS) were determined in a group of biologically active peptides (molecular wt range 1.3 - 3.3 kDa). The ESI response is dependent on type of organic solvent in the mobile phase mixture and therefore, solvent choice affects optimal ion intensities. As expected, intact peptide ions gave a more intense ESI signal in polar protic solvent mixtures than in the low polarity solvent. However, for four out of the five analysed peptides, neither the ESI response nor the CSD were affected by the volatility of the solvent mixture. Therefore, in solvent mixtures, as the composition changes during the evaporation processes, the $pK_b$ of the amino acid composition is a better predictor of multiple charging of the peptides.