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Kinetic Study on Nucleophilic Displacement Reactions of Y-Substituted-Phenyl 2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Effects of Modification of 2-MeO in Benzoyl Moiety by 2-Me on Reactivity and Reaction Mechanism

  • Lee, Ji-Youn;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3795-3799
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    • 2013
  • The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

Photodegradability of Blends of Polystyrene and Vinyl Ketone Polymers (비닐 케톤계 고분자와 폴리스티렌 블렌드의 광분해성)

  • Kim, Jeong Ho
    • Clean Technology
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    • v.4 no.2
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    • pp.54-60
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    • 1998
  • Polyphenylvinylketone (PPVK) having a carbonyl group at the side chain was blended with polystyrene (PS) to investigate the effect of vinylketone polymers on the photodegradability of the blend as a function of U.V. irradiation time. Hydrogenated polyphenylvinylketone (PPVK(H)) which is made by hydrogenation of some of the carbonyl groups in PPVK was also blended with PS to check the role of carbonyl carbonyl group in the process of photodegradation. Photodegradability was also investigated for blends of PS with polymethylvinylketone (PMVK) and for copolymers of styrene and methylvinylketone (SMVK) to compare the effect of copolymerization versus blending on photodegradability. PPVK showed higher photodegradability than PPVK(H), which followed that the blends of PS with PPVK gave higher degradability than with PPVK(H). In view of the fact that PPVK(H) is a partially hydrogenated version of PPVK, carbonyl group was confirmed to be involved in the photodegradation mechanism. When polymethylvinylketone (PMVK) was blended with PS, this blend showed a higher degradability than PS/PPVK blend. Therefore the highest photodegradability was achieved when PS was blended with PMVK followed by PPVK and PPVK(H) in order. When SMVK was UV irradiated, it showed the highest photodegradability than any blends mentioned above. Therefore, copolymerization was proved to be the better means of photodegradation than blending.

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Effect of Reduced Graphite Oxide as Substrate for Zinc Oxide to Hydrogen Sulfide Adsorption

  • Jeon, Nu Ri;Song, Hoon Sub;Park, Moon Gyu;Kwon, Soon Jin;Ryu, Ho Jeong;Yi, Kwang Bok
    • Clean Technology
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    • v.19 no.3
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    • pp.300-305
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    • 2013
  • Zinc oxide (ZnO) and reduced graphite oxide (rGO) composites were synthesized and tested as adsorbents for the hydrogen sulfide ($H_2S$) adsorption at mid-to-high (300 to $500^{\circ}C$) temperatures. In order to investigate the critical roles of oxygen containing functional groups, such as hydroxyl, epoxy and carboxyl groups, attached on rGO surface for the $H_2S$ adsorption, various characterization methods (TGA, XRD, FT-IR, SEM and XPS) were conducted. For the reduction process for graphite oxide (GO) to rGO, a microwave irradiation method was used, and it provided a mild reduction environment which can remain substantial amount of oxygen functional groups on rGO surface. Those functional groups were anchoring and holding nano-sized ZnO onto the 2D rGO surface; and it prevented the aggregation effect on the ZnO particles even at high temperature ranges. Therefore, the $H_2S$ adsorption capacity had been increased about 3.5 times than the pure ZnO.

Synthesis of Trimetallic (PtRu-Sn/VC, PtRu-Ni/VC) Catalysts by Radiation Induced Reduction for Direct Methanol Fuel Cell (DMFC) (방사선환원법을 이용한 직접메탄올연료전지용(DMFC) 삼성분계촉매(PtRu-Sn/VC, PtRu-Ni/VC)의 합성)

  • Kim, Sang Kyum;Park, Ji Yun;Hwang, Sun Choel;Lee, Do Kyun;Lee, Sang Heon;Rhee, Young Woo;Han, Moon Hee
    • Clean Technology
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    • v.19 no.3
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    • pp.320-326
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    • 2013
  • Nano-sized PtRu-Ni/VC and PtRu-Sn/VC electrocatalysts were synthesized by a one-step radiation-induced reduction (RIR) (30 kGy) process using distilled water as the solvent and Vulcan XC-72 as the supporting material. The obtained electrocatalysts were characterized by transmission electron microscopy (TEM), scanning electron microscope energy dispersive spectroscopic (SEM-EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The catalytic efficiency of electrocatalysts was examined for oxygen reduction, MeOH oxidation and CO stripping decreased in the following order, Hydrogen stripping : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/VC$^{(R)}$ (E-TEK). MeOH oxidation : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/ VC$^{(R)}$ (E-TEK). Unit cell performance : PtRu-Sn/VC > PtRu-Ni/VC > PtRu/VC$^{(R)}$ (E-TEK) catalysts.

A Green Preparation of Drug Loaded PAc-β-CD Nanoparticles from Supercritical Fluid (초임계 유체를 이용한 약물이 담지된 PAc-β-CD 나노 입자의 친환경적인 제조)

  • Jang, Min Ki;Kim, Yong Hun;Kim, Dong Woo;Lee, Si Yun;Lim, Kwon Taek
    • Clean Technology
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    • v.26 no.1
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    • pp.1-6
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    • 2020
  • Rapid expansion of supercritical solution (RESS) process was used to make molsidomine (MOL) loaded peracetyl-β-cyclodextrin (PAc-β-CD) nanoparticles, which were collected into the air. The effect of the concentration of the drug PAc-β-CD (0.5 and 1 wt%), extraction temperature (45 ~ 60 ℃), nozzle length (5 ~ 20 mm) and internal diameter (ID) (50 ~ 150 μm) of a capillary, and spray distance on the particle size and morphology of the resulting particles were investigated. The interaction of a drug and PAc-β-CD was confirmed by 1H-NMR spectroscopy while the particle size was measured by means of a scanning electron microscope. It was found that increasing the temperature from 45 ℃ to 60 ℃ and decreasing the nozzle diameter from 150 μm to 50 μm had an increasing effect on the average particle size, while increasing the spray distance led to a decrease in the average particle size at a constant pressure of 34.5 MPa and temperature of 45 ℃. With 0.5 wt% of PAc-β-CD, the capillary nozzle of short length (5 mm) and small ID (50 μm) gave the smallest size (165 nm). The obtained nanoparticles showed increased dispersity and solubility in oil. The oil suspension of the inclusion complex showed increased sustainability, which can increase the in-vitro controlled release time of the drug.

Effects of TGF-$\beta$3 on Epithelial-mesenchymal transformation and Epidermal growth factor receptor expression in palatogenesis of chicken embryo (계태아 발생시 TGF-$\beta$3가 구개판 내측돌기상피의 상피간엽변환 및 상피성장인자수용체 발현에 미치는 영향)

  • Yang Byoung-Eun;Lee Jong-Ho
    • Korean Journal of Cleft Lip And Palate
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    • v.4 no.1
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    • pp.13-26
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    • 2001
  • Cleft lip and/or palate is the congenital orofacial malformation most commonly occurred in humans, The disease is multifactorial and is probably caused by genetic and/or environmental factors, So, there are many problems in research concerning etiology and in treatment of the disease, Even the most practiced and sophisticated methods of surgical repair are necessarily followed by scar contraction and fibrosis, which result in skeletal defects, dental abnormalities, cosmetic disfigurement, and speech impairment, As a result, Fetal surgery can be considered but practiced rarely when the deformity is not fatal to life, And treatment of cleft palate is performed in the form of medicine projection into uterus in animal experiments, Many studies show that growth factor and its receptor emerge from the developing palate; and the epidermal growth factor receptors have a important role in craniofacial development and in palatal fusion, The palatal morphogenesis of the avine is different from the mammal's; it takes the form of physiologic cleft palate, Recently, cleft palate fusion experiment was performed when the avine were in the period of palate formation through the exogenous TGF-β3 addition, and it showed that the exogenous TGF-β3 makes fusion of divided palate through certain process when cleft palate is occurred in palatal formation, In this study, I had the conformation of the fusion of cleft palate through the addition of TGF-β in case of chicken embryo, and observed the effect of TGF-β in EGF receptor distribution, And the following is the results of this study, 1. In case of the TGF-βl and β3 addition group, there was the decrease of EGFR(Epidermal Growth Factor Receptor) immunoreactivity in mesenchymal cells beneath the medial edge epithelium and also in epithelial mesenchymal interface which is between medial edge epithelium and nasal septum in 72 hours, 2, The immunoreactivity of the control group resembles that of normal chicken embryo palate in development, 3. In the view through fluorescence confocal microscopy, there was confluence in TGF-β3 addition group, This shows that the confluence induced by exogenous TGF-β3 is related to EGFR expression in palate of chicken embryo, which is a physiologic cleft palate model.

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Reduction of the Odors during Pig Manure Composting Using of Pyroligneous Acid Liquor (목초액 처리가 돈분 퇴비화 과정중 악취저감에 미치는 영향)

  • Lee, Jong-Eun;Chang, Ki-Woon;Lee, Jong-Jin;Hwang, Joon-Young
    • Korean Journal of Agricultural Science
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    • v.32 no.2
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    • pp.233-241
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    • 2005
  • The objective of this study was to investigate the effect of odor removal such as $NH_3$, volatile organic acid (VOA) during the pig manure composting using of the Pyroligneous acid liquor (PAL). The odor removal efficiencies were evaluated throughout the dilution rates (${\times}0$, ${\times}100$, ${\times}300$) of PAL. The results of the study are as followings. $NH_3$ content in all treatments (volume 10L) was approximately 8 mg/kg in compost piles on the first day. In the case of control treatment, it was increased by 46 mg/kg within 10 days and was not detected after 25 days. In contrast, those levels in PA-100 and PA-300 treatments were similar values at 38 mg/kg within 6 days and decreased after 15 days. And GC. equipment was used to analyze the volatile organic acids (acetic acid, butyric acid, isobutyric acid, isovaleric aicd, 2,3-methylbutyric aicd, and propionic acid). The concentration of acetic acid and butyric acid were the higher than other VOAs during the initial composting day and sharply declined after 15 days. The VOAs in the control treatment were detected until 40 days, but PA-100 and PA-300 treatments were not measured after 15 days. The PA-100 in all treatments was the most effective treatment for $NH_3$ gas and VOAs reduction during composting. In addition, these studies for the odor reduction in compost manufacture process would have to research on more effective methods for the PAL utilization in agro-biological aspects.

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The distribution and antimicrobial susceptibility of pathogenic microorganisms isolated from chicken slaughtering and processing procedure (닭 도계 및 가공공정 중 유해미생물의 분포와 항생제 감수성)

  • Seol, Kuk-Hwan;Kim, Ki Hyun;Jo, Su-Mi;Kim, Young Hwa;Kim, Hyun-Wook;Ham, Jun-Sang
    • Korean Journal of Agricultural Science
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    • v.42 no.1
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    • pp.29-35
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    • 2015
  • This study was performed to analyze the distribution and antimicrobial resistance of pathogenic microorganisms isolated from the carcass and environments of chicken processing plant located in Gyeonggi province from October to November in 2010. Chicken slaughterhouse was visited 3 times and totally 40 samples were collected from chicken carcass before and after washing (n=14), chicken cuts (n=7), cooling water (n=8), brine (n=2), cutting knives (n=7) and working plate (n=2). Whole-chicken rinsing technique (for chicken carcasses) and swab technique (for working plate and knives) were used to analyze the distribution of pathogenic microorganisms. In addition, brine and chilling water from storage tanks were gathered using sterilized tubes and used as samples. The matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for whole cell fingerprinting in combination with a dedicated bioinformatic software tool was used to identify the isolated microorganisms. The pathogenic microorganisms, such as Bacillus cereus (n=8) and Staphylococcus aureus (n=9), were isolated form the chicken processing process (chicken carcasses of before and after chilling, chicken cuts, and working plate). The antimicrobial susceptibility of those isolated microorganisms was analyzed using 21 antimicrobial agents. In the case of B. cereus, it showed 100% of resistance to subclasses of penicillins and peptides, and it also resistant to cephalothin, a member of critically important antimicrobials (CIA), however there was no resistance (100% susceptible) to vancomycin and chloramphenicol. S. aureus showed 100% resistance to subclasses of peptides and some of penicillins (penicillin and oxacillin), however, it showed 100% susceptibility to cephalosporins (cefazolin and cephalothin). All of the tested pathogens showed multi drug resistance (MDR) more than 4 subclasses and one of B. cereus and S. aureus showed resistance to 9 subclasses. After the ban on using the antimicrobials in animal feed in July 2011, there would be some change in microbial distribution and antimicrobial resistance, and it still has a need to be analyzed.

LRFD Design and Reliability Level Estimation of a Steel Closed-Box Girder Bridge (폐단면 강박스거더교의 LRFD 설계와 신뢰성수준 평가)

  • Huh, Jung-Won;Yun, Dong-Geon
    • Journal of the Computational Structural Engineering Institute of Korea
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    • v.23 no.2
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    • pp.217-225
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    • 2010
  • Most of the steel bridges in Korea are being currently designed by the allowable stress design method that uses the conventional deterministic factors of safety. However the limit state design based on the concept of probability, statistics and reliability engineering is becoming very popular as a global standard deign method, leading the rational and economic bridge design. As part of the fundamental research to establish the load and resistance factor design(LRFD) of steel bridges considering domestic environmental conditions and regional characteristics, an experimental design is conducted by applying AASHTO-LRFD specification especially to a steel closed-box girder, which occupies relatively a large portion of steel bridges in Korea. Throughout the experimental design according to various sectional changes, some of the issues to be considered in the LRFD design of a composite steel closed-box girder bridge are examined. In this process, an Excel-based design verification program is developed for easy computation and prevention of errors. Quantitative reliability levels of the bridge sections designed by LRFD are also estimated using a reliability analysis method, and compared with the target reliability indexes applied in the LRFD design to verify the validity of the procedure and methodology used in this study.

Ultrasonic Wave Propagation Analysis for Damage Detection in Heterogeneous Concrete Materials (콘크리트 내부결함 탐지를 위한 초음파 전파 해석)

  • Jung, Hwee Kwon;Rhee, Inkyu;Kim, Jae-Min
    • Journal of the Computational Structural Engineering Institute of Korea
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    • v.33 no.4
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    • pp.225-235
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    • 2020
  • Ultrasonic investigation of damage detection has been widely used for non-destructive testing of various concrete structures. This study focuses on damage detection analysis with the aid of wave propagation in two-phase composite concrete with aggregate (inclusion) and mortar (matrix). To fabricate a realistic simulation model containing a variety of irregular aggregate shapes, the mesh generation technique using an image processing technique was proposed. Initially, the domains and boundaries of the aggregates were extracted from the digital image of a typical concrete cut-section. This enables two different domains: aggregates and mortar in heterogeneous concrete sections, and applied the grids onto these domains to discretize the model. Subsequently, finite element meshes are generated in terms of spatial and temporal requirements of the model size. For improved analysis results, all meshes are designed to be quadrilateral type, and an additional process is conducted to improve the mesh quality. With this simulation model, wave propagation analyses were conducted with a central frequency of 75 kHz of the Mexican hat incident wave. Several void damages, such as needle-shaped cracks and void-shaped holes, were artificially introduced in the model. Finally, various formats of internal damage were detected by implementing energy mapping based signal processing.