• Title/Summary/Keyword: Dual solvent

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Limitations of the Transition State Variation Model. Part 8. Dual Reaction Channels for Solvolyses of 3,4-Dimethoxybenzenesulfonyl Chloride

  • Koo, In-Sun;Kwon, Eun-Ju;Choi, Ho-June;Yang, Ki-Yull;Park, Jong-Keun;Lee, Jong-Pal;Lee, Ikc-Hoon;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2377-2381
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    • 2007
  • Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

Effect of Solvents on Physical Properties and Release Characteristics of Monolithic Hydroxypropylmethylcellulose Matrix Granules and Tablets

  • Cao Qing-Ri;Choi Yun-Woong;Cui Jing-Hao;Lee Beom-Jin
    • Archives of Pharmacal Research
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    • v.28 no.4
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    • pp.493-501
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    • 2005
  • Effect of solvents on physical characteristics and release characteristics of monolithic acetaminophen (APAP) hydroxypropylmethylcellulose (HPMC) matrix granules and tablets were examined. Various types and amounts of solvents were employed for granulation and coating. APAP and other excipients were mixed and were then wet-granulated in a high-speed mixer. The dried granules were then directly compressed and film-coated with low viscosity grade HPMC. As the amount of water increased, the size of granules also increased, showing more spherical and regular shape. However, manufacturing problems such as capping and lamination in tableting occurred when water was used alone as a granulating solvent. The physical properties of HPMC matrix granules were not affected by the batch size. The initial release rate as well as the amount of APAP dissolved had a tendency to decrease as the water level increased. Addition of nonaqueous solvent like ethanol to water resulted in good physical properties of granules. When compared to water/ethanol as a coating solvent, the release rate of film-coated HPMC matrix tablets was more sensitive to the conditions of coating and drying in methylene chloride/ethanol. Most of all, monolithic HPMC matrix tablet when granulated in ethanol/water showed dual release with about $50\%$ drug release immediately within few minutes followed by extended release. It was evident that the type and amount of solvents (mainly water and ethanol) were very important for wet granulation and film-coating of monolithic HPMC matrix tablet, because the plastic deforming and fragmenting properties of material were changed by the different strengths of the different solvents.

Limitations of the Transition State Variation Model(5) Dual Reaction Channels for Solvolysis of Dansyl Chloride

  • Koo In Sun;Lee Ocg-Kyeong;Lee Ikchoon
    • Bulletin of the Korean Chemical Society
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    • v.13 no.4
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    • pp.395-398
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    • 1992
  • Rate of solvolysis of dansyl chloride in aqueous binary mixtures of acetone, methanol and ethanol are reported. Kinetic solvent isotope effects in methanol and product selectivities in alcohol-water mixtures are also reported. Kinetic data are interpreted with the Grunwald-Winstein and Kivinen equations. The value of $k_{CH3OH}/k_{CH3OD}=1.76$ suggests that a general have catalyzed and/or an $S_AN$ pathway is operative in methanol, a less polar solvent. Rate-rate profiles for solvolysis of dansyl chloride in the aqueous binary media indicate a change in reaction channel from $S_AN$ (in less polar media) to $S_N2$ (in more polar media) mechanism.

Kinetic and Thermodynamic Analysis of AChE Inhibition of Solvent Extract Fractions from Inonotus obliquus (차가버섯 용매추출분획의 Acetylcholinesterase 저해활성에 대한 동역학 및 열역학적 해석)

  • Kim, Hak-Kyu;Hur, Won;Hong, Eok Kee;Lee, Shin-Young
    • Food Engineering Progress
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    • v.15 no.4
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    • pp.289-296
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    • 2011
  • Twenty four fractions by solvent extraction and/or acid precipitation from fruit body and culture broth of Inonotus obliquus were prepared, and their inhibitory effect against acetylcholinesterase (AChE) was investigated. Among these fractions, acid (1 M HCl) precipitates from cell-free culture broth and fruit body exhibited the highest inhibitory effect on AChE in vitro. Acid precipitates inhibited AChE activity in a concentration-dependant manner and $IC_{50}$ values of both acid precipitates were 0.53 mg/mL. The inhibition pattern was general non-competitive inhibition. The energetic parameters were also determined by dual substrate/temperature design. Both acid precipitates increased the values of Ea, ${\Delta}H,/;{\Delta}G$ and ${\Delta}H^{\ast}$ decreasing the value of ${\Delta}S$ for AChE. The results implied that the acid precipitates from I. obliquus increased the thermodynamic barrier, leading to the breakdown of ES complex and the formation of products as inhibitory mechanism.

Interpretation of Dispersion Phenomena in Grunwald-Winstein Correlation for Solvolyses of Naphthoyl Chloride

  • Ryu, Zoon-Ha;Ju, Chang-Suk;Sung, Dae-Dong;Sung, Nak-Chang;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.123-131
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    • 2002
  • Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).

A Patterning Process for Organic Thin Films Using Discharge and Suction Needles (토출 및 흡입 Needle을 이용한 유기 박막 패터닝 공정)

  • Kim, Daeyeob;Shin, Dongkyun;Lee, Jinyoung;Park, Jongwoon
    • Journal of the Semiconductor & Display Technology
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    • v.19 no.1
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    • pp.79-84
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    • 2020
  • Unlike a printing process, it is difficult to pattern organic thin films in the longitudinal (coating) direction using a coating process. In this paper, we have investigated the feasibility of patterning organic thin films using needles. To this end, we have slot-coated an aqueous poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) solution in the form of a fine stripe or large area and then applied the dual needle; one for discharging the main solvent of the underlying thin film and the other for sucking the dissolved thin film. We have found that the pattern width and depth increase as the moving speed of the plate decreases. However, it is observed that the sidewall slope is very gentle (the length of the slope is of the order of 200 ㎛) due to the fact that the discharged main solvent is widely spread and then isotropic etching occurs. With this scheme, we have also demonstrated that a fine stripe can be obtained by scanning the dual needle closely. To demonstrate its applicability to solution-processable organic light-emitting diodes (OLEDs), we have also fabricated OLED with the patterned PEDOT:PSS stripe and observed the insulation property in the strong light-emitting stripe.

Antagonism and Structural Identification of Antifungal Compound from Chaetomium cochliodes against Phytopathogenic Fungi

  • Kang, Jae Gon;Kim, Keun Ki;Kang, Kyu Young
    • Journal of Applied Biological Chemistry
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    • v.42 no.3
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    • pp.146-150
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    • 1999
  • As a part of the integrated disease system in greenhouse, an antifungal fungus(AF1) was isolated from greenhouse soil. It exhibited strong inhibitory activites against Pythium ultimum, Phytophtora capsici, Rhizoctonia solani, Botrytis cinerea, and Fusarium oxysporum based on dual culture on 1/5 strength of potato dextrose agar between antagonistic fungus and several plant pathogens. The antagonistic fungus was identified as Chaetomium cochliodes, based on morphological characteristics; the body of the perithecium bears straight or slightly wavy, unbranched hairs, whilst the apex bears a group of spirally coiled hairs. To investigate antagonistic principles, antifungal compound was extracted and fractionated by different solvent systems. An antifungal compound was isolated as pure crystal from is culture filtrate using organic solvent extraction and column chromatography, followed by preparative thin layer chromatography. The chemical structure of the purified antifungal compound was identified as chaetoglobosin A based on the data obtained form $^1H-NMR$, $^{13}C-NMR$, DEPT 90, 135, $^1H-^1H$ COSY, $^1H-^{13}C$ COSY and EI/MS. $ED_{50}$ values of the chaetoglobosin A against P. ultimum, P. capsici, R. solani, B. cinerea and F. oxysporum were 1.98, 4.01, 4.16, 2.67 and 35.14 ppm, respectively.

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Electrical Characteristics of Solution Processed DAL TFT with Various Mol concentration of Front channel

  • Kim, Hyunki;Choi, Byoungdeog
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.211.2-211.2
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    • 2015
  • In order to investigate the effect of front channel in DAL (dual active layer) TFT (thin film transistor), we successfully fabricated DAL TFT composed of ITZO and IGZO as active layer using the solution process. In this structure, ITZO and IGZO active layer were used as front and back channel, respectively. The front channel was changed from 0.05 to 0.2 M at fixed 0.3 M IGZO of back channel. When the mol concentration of front channel was increased, the threshold voltage (VTH) was increased from 2.0 to -11.9 V and off current also was increased from 10-12 to 10-11. This phenomenon is due to increasing the carrier concentration by increasing the volume of the front channel. The saturation mobility of DAL TFT with 0.05, 0.1, and 0.2 M ITZO were 0.45, 4.3, and $0.65cm2/V{\cdot}s$. Even though 0.2 M ITZO has higher carrier concentration than 0.05 and 0.1 M ITZO, the 0.1 M ITZO/0.3 M IGZO DAL TFT has the highest saturation mobility. This is due to channel defect such as pores and pin-holes. These defect sites were created during deposition process by solvent evaporation. Due to these defect sites, the 0.1 M ITZO/0.3 M IGZO DAL TFT shows the higher saturation mobility than that of DAL TFT with front channel of 0.2 M ITZO.

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Preparations and Antistatic/UV Blocking Properties of Dual Functional Phthalocyanine Materials (기능성 프탈로시아닌 물질의 제조 및 대전방지/UV 차단 특성)

  • Kang, Young-Goo;Ihm, Dae-Woo;Kim, Shi-Surk;Park, Byoung-Ki
    • Journal of the Korean Society of Safety
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    • v.23 no.1
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    • pp.66-71
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    • 2008
  • A new route to phthalocyanine complexes were developed to synthesize these products by fusion in the absence of solvent. This new method of synthesis without using solvent has advantages over the conventional synthetic methods since there are no risk of explosion and formation of harmful vapor from organic solvent. Reaction of PcFe with axial ligands such as $PcFe(4-VP)_2$[Pc: Phthalocyanine, 4-VP: 4-Vinylpyridine] and $PcFe(VIM)_2$[VIM: 1-Vinylimidazole] afforded powderlike, pure dark greenish blue colored products. The resulted products are soluble in $CH_2Cl_2$ and found to be complexes of the type $PcFeL_2$. Spectral properties were studied with ATR-FTIR and UV/Vis. Thermal and electrical characterization was also performed. Phthalocyanine complexes exhibit useful properties such as UV/Vis blocking, antistatic characteristics and excellent thermal stability and we anticipate various applicability in numerous products.

A LiPF6-LiFSI Blended-Salt Electrolyte System for Improved Electrochemical Performance of Anode-Free Batteries

  • Choi, Haeyoung;Bae, YeoJi;Lee, Sang-Min;Ha, Yoon-Cheol;Shin, Heon-Cheol;Kim, Byung Gon
    • Journal of Electrochemical Science and Technology
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    • v.13 no.1
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    • pp.78-89
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    • 2022
  • ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF6 + 3.8 M lithium bis(fluorosulfonyl)imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO3 additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO4/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.