• Title/Summary/Keyword: Stepwise reaction

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Synthesis and Characterization of Cellulose-Hybrid Polystyrene Nanoparticles by Using Reactive Hydroxypropyl Methylcellulose Phthalate (반응형 히드록시프로필 메틸셀룰로오스 프탈레이트를 이용한 셀룰로오스 혼성 폴리스티렌 나노입자의 합성 및 특성 분석)

  • Cheong In-Woo
    • Polymer(Korea)
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    • v.30 no.5
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    • pp.437-444
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    • 2006
  • Reactive hydroxypropyl methylcellulose phthalate (reactive HPMCP) was synthesized by using a stepwise urethane reaction with isophorone diisocyanate (IPDI) and 2-hydroxyethyl moth acrylate (HEMA). Molecular weight, acid number, and critical micelle concentration (CMC) of the synthesized reactive HPMCP and pristine HPMCP were measured and used as a polymeric surfactant in the emulsion polymerizations of styrene. In the preparation of HPMCP-hybrid poly styrene nanoparticles, 6, 9, 12, 18, and 24 wt% of HPMCPs were introduced, and the maximum rate of polymerization ($R_{p,max}$), the average number of radicals per particle (n), particle size distribution were investigated. In addition, core - shell morphology of the nanoparticles were observed by using TEM and their thermal stabilities were measured by using TGA. Reactive HPMCP showed higher $R_{p,max}$, smaller particle size, larger values of n and gel contents as compared with pristine HPMCP, due to the vinyl groups from HEMA, which can be reacted with styrene oligomers, in the reactive HPMCP.

Kinetic Study on Nucleophilic Displacement Reactions of 2-Chloro-4-Nitrophenyl X-Substituted-Benzoates with Primary Amines: Reaction Mechanism and Origin of the α-Effect

  • Um, Tae-Il;Kim, Min-Young;Kim, Tae-Eun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.436-440
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    • 2014
  • The ${\alpha}$-Effect; Ground state; Transition state; Intramolecular H-bonding; Yukawa-Tsuno plot; Second-order rate constants for aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (1a-h) have been measured spectrophotometrically in 80 mol % $H_2O/20$ mol % DMSO at $25.0^{\circ}C$. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (1d) with a series of primary amines curves downward, which has been taken as evidence for a stepwise mechanism with a change in rate-determining step (RDS). The Hammett plots for the reactions of 1a-h with hydrazine and glycylglycine are nonlinear while the Yukawa-Tsuno plots exhibit excellent linearity with ${\rho}_X=1.22-1.35$ and ${\gamma}= 0.57-0.59$, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by stabilization of substrates possessing an electron-donating group (EDG) through resonance interactions between the EDG and C=O bond of the substrates. The ${\alpha}$-effect exhibited by hydrazine increases as the substituent X changes from a strong EDG to a strong electron-withdrawing group (EWG). It has been concluded that destabilization of hydrazine through the electronic repulsion between the adjacent nonbonding electrons is not solely responsible for the substituent dependent ${\alpha}$-effect but stabilization of the transition state is also a plausible origin of the ${\alpha}$-effect.

Kinetic Study on Aminolysis of Y-Substituted-Phenyl X-Substituted-Benzoates: Effects of Substituents X and Y on Reactivity and Reaction Mechanism

  • Jeon, Seong Hoon;Kim, Hyun Soo;Han, Young Joon;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.471-476
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    • 2014
  • A kinetic study on aminolysis of 2-chloro-4-nitrophenyl X-substituted-benzoates (2a-k) in 80 mol % $H_2O/_20mol%$ DMSO at $25.0^{\circ}C$ is reported. The Br${\emptyset}$nsted-type plot for the reactions of 2-chloro-4-nitrophenyl benzoate (2g) with a series of cyclic secondary amines curves downward (e.g., ${\beta}_1=0.25$, ${\beta}_2=0.85$ and $pK_a^o=10.3$), which is typical of reactions reported to proceed through a stepwise mechanism with a change in ratedetermining step (RDS). The Hammett plot for the reactions of 2a-k with piperidine consists of two intersecting straight lines, while the corresponding Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X=1.15$ and r = 0.59. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in RDS but is caused by stabilization of substrates through resonance interactions between the electron-donating substituent and the C=O bond. Substrates possessing a substituent at the 2-position of the leaving aryloxide deviate negatively from the curved Br${\emptyset}$nsted-type plot for the reactions of Y-substituted-phenyl benzoates (3a-i), implying that the steric hindrance exerted by the substituent at the 2-position is an important factor which governs the reactivity of Y-substituted-phenyl benzoates.

Aminolysis of 2,4-Dinitrophenyl 2-Furoate and 2-Thiophenecarboxylate: Effect of Modification of Nonleaving Group from Furoyl to Thiophenecarbonyl on Reactivity and Mechanism

  • Um, Ik-Hwan;Min, Se-Won;Chuna, Sun-Mee
    • Bulletin of the Korean Chemical Society
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    • v.29 no.7
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    • pp.1359-1363
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    • 2008
  • Second-order rate constants have been determined spectrophotometrically for reactions of 2,4-dinitrophenyl 2- thiophenecarboxylate (2) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Brønsted-type plot exhibits a downward curvature, i.e., the slope decreases from 0.74 to 0.34 as the amine basicity increases. The $pK_a$ at the center of the Brønsted curvature, defined as $pK_a^o$, has been determined to be 9.1. Comparison of the Brønsted-type plot for the reactions of 2 with that for the corresponding reactions of 2,4-dinitrophenyl 2-furoate (1) suggests that reactions of 1 and 2 proceed through a common mechanism, although 2 is less reactive than 1. The curved Brønsted-type plot has been interpreted as a change in RDS of a stepwise mechanism. The replacement of the O atom in the furoyl ring by an S atom (1 $\rightarrow$ 2) does not alter the reaction mechanism but causes a decrease in reactivity. Dissection of the apparent second-order rate constants into the microscopic rate constants has revealed that the $k_2/k_{-1}$ ratio is not influenced upon changing the nonleaving group from furoyl to thiophenecarbonyl. However, $k_1$ has been calculated to be smaller for the reactions of 2 than for the corresponding reactions of 1, indicating that the C=O bond in the thiophenecarboxylate 2 is less electrophilic than that in the furoate 1. The smaller k1 for the reactions of 2 is fully responsible for the fact that 2 is less reactive than 1.

Job Stress Levels in Environment Impact Assessment, and Related Factors Including Expert (환경영향평가 전문가의 직무스트레스 수준 및 관련 요인)

  • Ji, Dong-Ha;Jeon, Hye-Ri;Choi, Soo-Hyun;Son, Bu-Soon;Choi, Mi-Suk
    • Journal of Environmental Health Sciences
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    • v.36 no.5
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    • pp.373-382
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    • 2010
  • A number of recent studies have shown that occupational stress is closely associated with increased fatigue and decreased job satisfaction. This study was designed to assess stress in workers in the field of EIA (environment impact assessment) from July 2009 through september 2009, and questionnaires were uesd to analyze the stress scores and identify the primary factors influencing stress in this occupation. The number of respondents was 272 working in the Capital (Seoul and Kyunggido), Chungcheongdo, Jejudo area. A structured questionnaire was used to evaluate the participants' socio-demographics, job-related factors, health-related behaviors, occupational stress, reaction factor (self-perceived fatigue, job satisfaction) and buffer factor (social support). Occupational stress and self-perceived fatigue were assessed using the Korean Occupational Stress Scale-Short Form (KOSS-SF) and the Multidimensional Fatigue Scale (MFS), respectively. The analysis revealed a strong correlation between occupational stress, job satisfaction, and social support, with occupational stress being associated with an increased risk of fatigue and decreased job satisfaction. In the multiple regression analysis(stepwise), the main factors influencing occupational stress were found to be job satisfaction, supervisor, fatigue, working time, no. of personnel, career. The results of this study suggest that occupational stress is a determinant predictor of self perceived fatigue and job satisfaction. Thus, a strong recommendation is made for a stress management program for reduction of occupational stress, and for the development of relevant experts on the health and quality of life of environment impact assessment workers.

Role of Features in Plasma Information Based Virtual Metrology (PI-VM) for SiO2 Etching Depth (플라즈마 정보인자를 활용한 SiO2 식각 깊이 가상 계측 모델의 특성 인자 역할 분석)

  • Jang, Yun Chang;Park, Seol Hye;Jeong, Sang Min;Ryu, Sang Won;Kim, Gon Ho
    • Journal of the Semiconductor & Display Technology
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    • v.18 no.4
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    • pp.30-34
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    • 2019
  • We analyzed how the features in plasma information based virtual metrology (PI-VM) for SiO2 etching depth with variation of 5% contribute to the prediction accuracy, which is previously developed by Jang. As a single feature, the explanatory power to the process results is in the order of plasma information about electron energy distribution function (PIEEDF), equipment, and optical emission spectroscopy (OES) features. In the procedure of stepwise variable selection (SVS), OES features are selected after PIEEDF. Informative vector for developed PI-VM also shows relatively high correlation between OES features and etching depth. This is because the reaction rate of each chemical species that governs the etching depth can be sensitively monitored when OES features are used with PIEEDF. Securing PIEEDF is important for the development of virtual metrology (VM) for prediction of process results. The role of PIEEDF as an independent feature and the ability to monitor variation of plasma thermal state can make other features in the procedure of SVS more sensitive to the process results. It is expected that fault detection and classification (FDC) can be effectively developed by using the PI-VM.

The relationship between myofiber characteristics and meat quality of Chinese Qinchuan and Luxi cattle

  • Lu, Xiao;Yang, Yuying;Zhang, Yimin;Mao, Yanwei;Liang, Rongrong;Zhu, Lixian;Luo, Xin
    • Animal Bioscience
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    • v.34 no.4
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    • pp.743-750
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    • 2021
  • Objective: The objectives of this study were to explore the expression patterns of myosin heavy chain (MyHC) genes of different skeletal muscles from Chinese cattle, and to investigate the relationship between myofiber characteristics and meat quality of M. longissimus lumborum (LL), M. psoas major (PM), and M. semimembranosus (SM) from Chinese Luxi and Qinchuan cattle. Methods: Three major muscles including LL, PM, and SM from Chinese Luxi cattle and Chinese Qinchuan cattle were used in this study. The myofiber characteristics were measured by histochemical analysis. The MyHC isoforms expression was evaluated by real-time quantitative polymerase chain reaction. Quality traits including pH value, meat color, cooking loss, Warner-Bratzler shear force (WBSF) and sarcomere length were determined at day 5 postmortem. Results: PM muscle had higher pH value, a* value, sarcomere length and lower WBSF value compared to LL and SM muscles (p<0.05). Numbers of type I myofiber and the relative expression of MyHC I mRNA in PM muscle were higher than those of LL and SM muscles (p<0.05). Myofiber diameter of PM muscle was lower than that of LL and SM muscles, regardless of myofiber types (p<0.05). Conclusion: According to the stepwise linear regression analyses, tenderness was influenced by myofiber characteristics in all three examined muscles. Tenderness of beef muscles from Qinchuan and Luxi cattle could be improved by increasing numbers of type I myofiber.

Conductance Study on the Characteristics of Solution Containing Crown Ethers and Univalent Cation Perchlorates

  • Lee, Shim-Sung;Park, Sung-Oh;Jung, Jong-Hwa;Lee, Bu-Yong;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.276-281
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    • 1990
  • The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

Potential Efficacy of Multiple-shot Long-pulsed 1,064-nm Nd:YAG in Nonablative Skin Rejuvenation: A Pilot Study

  • Kim, Young-Koo;Lee, Hae-Jin;Kim, Jihee
    • Medical Lasers
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    • v.9 no.2
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    • pp.159-165
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    • 2020
  • Background and Objectives The ultimate goal in current skin rejuvenation practice is to achieve a good result with minimal pain and downtime. Nonablative skin rejuvenation (NSR) is one technique. The efficacy of the long-pulsed 1064 nm Nd:YAG laser (LPNDY) has not been assessed in NSR. Materials and Methods Three target areas were selected (bilateral cheeks and glabellar region) in six volunteer subjects. A LPNDY with an integral skin temperature monitor delivered three stacked shots to each target area (1064 nm, 12 mm spot, 13 J/cm2, 1 Hz) without any skin cooling or anesthesia. The skin temperature was recorded before, during, and after each set of shots using the system monitor and in real-time using a high-sensitivity (±0.001℃) near-infrared video camera. The skin reaction was observed with the naked eye, and pain and discomfort were assessed by the subjects during and after treatment. Results The subjects reported a mild feeling of heat with no discomfort during or after the test treatments. Mild erythema was observed around the treatment areas, without noticeable edema. A series of three ascending skin temperature stepwise peaks, with a decrease in skin temperature towards the baseline after the third shot, was observed consistently. The mean temperatures for shots 1, 2, and 3 for the cheeks were 39.5℃, 42.0℃, and 44.4℃, respectively, and for the glabella, 40.8℃, 43.9℃, and 46.2℃, respectively. Similar ranges were indicated on the system integral temperature monitor. Conclusion A set of three stacked pulses with the LPNDY at a low fluence achieved ideal dermal temperatures to achieve some dermal remodeling but without any downtime or adverse events. The temperature data from the integral thermal sensor matched the video camera measurements with practical accuracy for skin rejuvenation requirements. These data suggest that LPNDY would satisfy the necessary criteria to achieve effective NSR, but further studies will be needed to assess the actual results in clinical practice.

Chimie Douce Reaction to Layered High-$T_c$ Superconducting / Super-ionic Conducting Heterostructures

  • Kim, Young-Il;Hwang, Seong-Ju;Yoo, Han-Ill;Choy, Jin-Ho
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.95-98
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    • 1998
  • We have developed new type of superconducting-superionic conducting nanohybrids, $Ag_xI_wBi_2Sr_2Ca_{n-1}Cu_nO_y$ (n=1 and 2) by applying the chimie douce reaction to the superconducting Bi-based cuprates. These nanohybrids can be achieved by the stepwise intercalation whereby the $Ag^+$ ion is thermally diffused into the pre-intercalated iodine sublattice of $IBi_2Sr_2Ca_{n-1}Cu_nO_y$. According to the X-ray diffraction analysis, the Ag-I intercalates are found to have an unique heterostructure in which the superionic conducting Ag-I layer and the superconducting $IBi_2Sr_2Ca_{n-1}Cu_nO_y$ layer are regularly interstratified with a remarkable basal increment of ~7.3$\AA$. The systematic XAS studies demonstrate that the intercalation of Ag-I accompanies the charge transfer between host and guest, giving rise to a change in hole concentration of $CuO_2$ layer and to a slight $T_c$ change. The Ag K-edge EXAFS result reveals that the intercalated Ag-I has a $\beta$-AgI-like local structure with distorted tetrahedral symmetry, suggesting a mobile environment for the intercalated $Ag^+$ ion. In fact, from ac impedance analyses, we have found that the Ag-I intercalates possess a fast ionic conductivity ($\sigma_i=10^{-1.4}\sim 10^{-2.6}\Omega^{-1}\textrm{cm}^{-1}\;at\;270^{\circ}C$ with an uniform activation energy ($\DeltaE_a=0.22\pm 0.02$ eV). More interesting finding is that these intercalates exhibit high electronic conducting as well as ionic ones ($t_i$=0.02~0.60) due to their interstratified structure consisting of superionic conducting and superconducting layers. In this respect, these new intercalates are expected to be useful as an electrode material in various electrochemical devices.

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