• Title/Summary/Keyword: chemical reagents

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The Effect of Polarizability on Rate and Reaction Mechanism: Reactions of S-Aryl Substituted Thiobenzoates with $HO-$ and Aryloxide Ions

  • Ik-Hwan Um;Sang-Eun Chun;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • v.12 no.5
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    • pp.510-514
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    • 1991
  • Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.

Factors Influencing S-O Bond and C-O Bond Cleavages in the Reactions of 2,4-Dinitrophenyl X-Substituted Benzenesulfonates with Various Nucleophilic Reagents

  • 엄익환;김정주;김명진;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.17 no.4
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    • pp.353-357
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    • 1996
  • Second-order rate constants have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with Z-substituted phenoxides in absolute ethanol at 25.0±0.1 ℃. The nucleophilic substitution reaction gives both S-O bond and C-O bond cleavage products. The extent of S-O bond cleavage increases significantly with increasing electron withdrawing ability of the sulfonyl substitutent X, while that of the C-O bond cleavage is independent on the electronic effect of the substituent. On the contratry, the effect of the substituent Z in the nucleophilic phenoxide is more significant for the C-O bond cleavage than for the S-O bond cleavage. Aminolyses of 2,4-dinitrophenyl benzenesulfonate (1) with various 1°, 2° and 3°amines have revealed that steric effect is little important. The extent of S-O bond cleavage increases with increasing the basicity of the amines, but decreases with increasing the basicity of the nucleophilic aryloxides, indicating that the HSAB principle is not always operative. Besides, reactant and solvent polarizability effect has also been found to be an important factor in some cases but not always to influence the reaction site.

Characterization and Antioxidant Activity of Gold Nanoparticles Synthesized using Bambusae Caulis in Taeniam extract (죽여 추출물로 합성한 금 나노 입자의 특성과 항산화 활성)

  • Park, Jin Oh;Park, Geuntae
    • Journal of Environmental Science International
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    • v.26 no.2
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    • pp.239-248
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    • 2017
  • Green synthesis of gold nanoparticles(GNPs) considered more ecofriendly and cost effective than other chemical methods use of dangerous reagents and solvents, improved material and energy efficiency and enhanced design of non-toxic products. In this study, we developed a green synthesis method for using Caulis in Taeniam (BCT). BCT were characterized by UV-vis, Zetasizer, TEM, XRD, and FTIR. The antioxidant activity of BCT was determined by DPPH and ABTS radical-scavenging assays, and heme oxygenase-1 induction in RAW 264.7 macrophages. The resulting BCT appeared spherical with an average diameter of 67.171.39 nm The aAntioxidant activity was increased in a dependent manner. To conclude, the green synthesis of BCT-GNPs was successful, and it appers to be useful in the for future applications.

Synthesis and Optically Characterization of CdSe Nanocrystal (CdSe 나노입자의 합성과 광학 특징)

  • Kim, Chanyoung;Kim, Sunghyun;Jung, Daehyuk
    • Journal of Integrative Natural Science
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    • v.1 no.3
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    • pp.250-253
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    • 2008
  • New issues arise as to surface characterization, quantification and interface formation. Surface and interface control of CdSe nanocrystal systems, one of the most studied and useful nanostructures. Semiconductor quantum dots (QDs) have been the subject of much interest for both fundamental reseach and technical applications in recent years, due mainly to their strong size dependent properties and excellent chemical processibility. In this dissertation, the synthesis of CdSe quantum dots were synthesized by pyrolysis of high-temperature organometallic reagents. In order to modify the size and quality of quantum dots, we controlled the growth temperature and the relative amount of precursors to be injected into the coordinating solvent. Moreover, an effective surface passivation of monodisperse nanocrystals was achieved by overcoating them with a higher-band-gap material. Synthesized CdSe quantum dots were studied to evaluate the optical, electronic and structural properties using UV-absorption, and photoluminescence measurement.

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A Study on the Effect of Chemicals on the Survival Rate and the Metamorphosis Speed in Rana nigromaculata Hallowell. (수종의 약품이 개구리의 생존율과 변태속도에 미치는 영향에 관한 연구)

  • 한양일;조소남
    • Journal of Environmental Health Sciences
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    • v.5 no.1
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    • pp.66-70
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    • 1978
  • This experiment is to search what some chemicals polluting water have an effect on the Rana nigromaculata Hallowell, in the survival rate and the metamorphosis speed from a tadpole to a young frog. 1. The fatal thickness by some agricultural chemicals and copper sulfate is different from one another. The fatal rate in the contrast group is 15 percent, and particulary Dithane M-45 is the most among the all reagents. 2. The effect on the anamorphosis is very severe. In the case of contrast group, it appears to stage 25, but it is not to appear at the group used agricultural chemicals. 3. The less the thickness of that is, the less the influence of the survival rate and the metamorphosis speed. 4. The density of the agricultural chemical is in inverse proportion to the survival rate and the metamorphosis speed, and the other side, the fatal rate is proportion.

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Experimental Determination of Equilibrium Constants of Copper Complexes in Aqueous Environment

  • Cho, Young-Il
    • Journal of Environmental Science International
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    • v.21 no.5
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    • pp.555-562
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    • 2012
  • The experimental determination of equilibrium constants is required to estimate concentrations of reagents and/or products in environmental chemical reactions. For an example, the choice of copper (Cu) complexation reactions was motivated by their fast kinetics and the ease of measurement of Cu by an ion-sensitive electrode. Each individual titrant of sulfate ($SO{_4}^{2-}$) and oxalate ($C_2O{_4}^{2-}$) was expected to have its own unique characteristics, depending on the bonding in Culigands connected to the aqueous species. The complexation reaction of Cu with $SO{_4}^{2-}$ somewhat fast reached equilibrium status compared with $C_2O{_4}^{2-}$. The experimental equilibrium constants ($K_{eq}$) of copper sulfate ($CuSO_4$) and copper oxalate ($CuC_2O_4$) were determined $10^{2.2}$ and $10^{3{\sim}4.3}$, respectively.

Desorption and Regeneration Characteristics for Previously Adsorbed Indium Ions to Phosphorylated Sawdust

  • Kwon, Taik-Nam;Jeon, Choong
    • Environmental Engineering Research
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    • v.17 no.2
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    • pp.65-67
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    • 2012
  • The desorption characteristics of previously adsorbed indium ions on phosphorylated sawdust were tested by various chemical reagents such as HCl, $HNO_3$, NaCl, ethylenediaminetetraacetic acid, and nitrilotriacetic acid. Among them, HCl was chosen as the best desorbing agent in terms of economics. The desorption efficiency of HCl for indium ions was about 97% at a concentration of 0.5 M. The desorption efficiency for indium ions was very high at about 94% even at a solid/liquid ratio of 10.0, and the desorption process was quickly performed within 60 min. The removal efficiency of indium ions in recycled phosphorylated sawdust could be maintained at 85% in the 4th cycle.

Temperature Measurements in a Microfluidic Chip with Polydiacetylene Sensor (폴리다이아세틸렌을 이용한 미세유동칩 내의 온도 측정)

  • Jang, Young-Sik;Ryu, Sung-Min;Song, Si-Mon
    • Proceedings of the KSME Conference
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    • 2008.11b
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    • pp.2696-2699
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    • 2008
  • Microfluidic chips have been frequently utilized to perform biochemical analysis, like cell culture, because they reduce the consumptions of analytes and reagents and automate multi-step analysis processes. It is often critical to monitor temperature in a microchannel for the analyses in order to control a reaction condition of bio or chemical molecules. We propose a novel method to monitor temperature of a microchannel flow by using polydiacetylene (PDA), a conjugated polymer, that has a unique property to transform its color from visible blue to fluorescent red by thermal stress. We inject PDA sensor droplets generated by hydrodynamic instability into a microchannel with a microheater incorporated on the channel bottom. Also, we change the channel temperature by providing the different electric power to the microheater. The results show that the florescence intensity of PDA sensor droplets linearly increases in response to the flow temperature increase within a certain range.

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Synthesis and Characterization of N,O-Carboxymethylchitosan Hydrogel Crosslinked by γ-ray Irradiation

  • Gwon, Hui-Jeong;Lim, Youn-Mook;An, Sung-Jun;Youn, Min-Ho;Nho, Young-Chang
    • Journal of Radiation Industry
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    • v.2 no.1
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    • pp.15-19
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    • 2008
  • In order to develop a water-solubility and biocompatibility, chemically modified chitosan, N,O-carboxymethylchitosan (NOCC), was synthesized and the NOCC hydrogels were prepared by using ${\gamma}-ray$ irradiation instead of chemical reagents. The FT-IR spectroscopy, swelling behavior, gel content and mechanical property such as gel strength of the hydrogel were measured. When the NOCC solution concentration was 15 wt% and the dose of irradiation was less than 50 kGy, the NOCC hydrogels had an excellent hydrophilicity and exhibited a good swelling behavior and mechanical properties.

Feasibility of On-chip Detection of Endotoxin by LAL Test

  • Lee, Eun-Kyu;Suh, Chang-Woo;Hwang, Sang-Youn;Park, Hyo-Jin;Seong, Gi-Hoon;Ahn, Yoo-Min;Kim, Yang-Sun
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.9 no.2
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    • pp.132-136
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    • 2004
  • The LAL (Limulus amebocyte lysate) test for the detection and quantification of endotoxin is based on the gelation reaction between endotoxin and LAL from a blood extract of Limulus polyphemus. The test is labor intensive, requiring dedicated personnel, a relatively long reaction time (approximately 1 h), relatively large volumes of samples and reagents and the detection of the end-point is rather subjective. To solve these problems, a miniaturized LOC (lab-on-a-chip) prototype, 62mm (L) ${\times}$ 18 mm (W), was fabricated using PDMS (polydimethylsiloxane) bonded to glass. Using this prototype, in which 2mm (W) ${\times}$ 44.3mm (L) ${\times}$ 100 $\mu\textrm{m}$ (D) microfluidic channel was constructed, turbidometric and chromogenic assay detection methods were compared, and the chromogenic method was found the most suitable for a small volume assay. In this assay, the kinetic-point method was more accurate than the end-point method. The PDMS chip thickness was found to be minimized to around 2 mm to allow sufficient light transmittance, which necessitated the use of a glass slide bonding for chip rigidity. Due to this miniaturization, the test time was reduced from 1 h to less than 10 min, and the sample volume could be reduced from 100 to ca. 4.4 ${\mu}$L. In summation, this study suggested that the LOC using the LAL test principle could be an alternative as a semi-automated and reliable method for the detection of endotoxin.