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Kinetics and Reaction Mechanism for Alkaline Hydrolysis of Y-Substituted-Phenyl Diphenylphosphinates

  • Hong, Hyo-Jeong;Lee, Jieun;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2001-2005
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    • 2013
  • The second-order rate constants ($k_{OH^-}$) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $OH^-$ in $H_2O$ at $25.0{\pm}0.1^{\circ}C$ have been measured spectrophotometrically. Comparison of $k_{OH^-}$ with $k_{EtO^-}$ (the second-order rate constants for the corresponding reactions with $EtO^-$ in ethanol) has revealed that $EtO^-$ is less reactive than $OH^-$ although the former is ca. 3.4 $pK_a$ units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Br${\o}$nsted-type plot for the reactions of 4a-4i with $OH^-$ is linear with ${\beta}_{lg}$ = -0.36. The Hammett plot correlated with ${\sigma}^-$ constants results in a slightly better correlation than that correlated with ${\sigma}^{\circ}$ constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ${\rho}$ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with $OH^-$ have been concluded to proceed through a concerted mechanism.

A Study of Crystallization and Fracture Toughness of Glass Ceramics in the ZrO2·SiO2 Systems Prepared by the Sol-Gel Method (졸-겔법으로 제조한 ZrO2·SiO2계 결정화 유리의 결정화 및 파괴인성에 관한 연구)

  • Shin, Dae-Yong;Han, Sang-Mok;Kang, Wie-Soo
    • Journal of Industrial Technology
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    • v.20 no.A
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    • pp.247-256
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    • 2000
  • Precursor gels with the composition of $xZrO_2{\cdot}(100-x)SiO_2$ systems (x=10, 20 and 30 mol%) were prepared by the sol-gel method. Kinetic parameters, such as activation energy, Avrami's exponent, n, and dimensionality crystal growth value, m, have been simultaneously calculated from the DTA data using Kissinger and Matusita equations. The crystallite size dependence on tetragonal to monoclinic transformation of $ZrO_2$ was investigated using XRD, in relation to the fracture toughness. The crystallization of tetragonal $ZrO_2$ occurred through 3-dimensional diffusion controlled growth(n=m=2) and the activation energy for crystallization was calculated using Kissinger and Matusita equations, as about $310{\sim}325{\pm}10kJ/mol$. The growth of $t-ZrO_2$, in proportion to the cube of radius, increased with increasing heating temperature and heat-treatment time. It was suggested that the diffusion of Zr4+ions by Ostwald ripening was rate-limiting process for the growth of $t-ZrO_2$ crystallite size. The fracture toughness of $xZrO_2{\cdot}(100-x)SiO_2$ systems glass ceramics increased with increasing crystallite size of $t-ZrO_2$. The fracture toughness of $30ZrO_2{\cdot}70SiO_2$ system glass ceramics heated at $1,100^{\circ}C$ for 5 h was $4.84Mpam^{1/2}$ at a critical crystaliite size of 40 nm.

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Synthesis and characterization of carbon doped TiO2 photocatalysts supported on stainless steel mesh by sol-gel method

  • Tijani, JO.;Fatoba, OO.;Totito, TC.;Roos, WD.;Petrik, LF.
    • Carbon letters
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    • v.22
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    • pp.48-59
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    • 2017
  • This study synthesized pure anatase carbon doped $TiO_2$ photocatalysts supported on a stainless steel mesh using a sol-gel solution of 8% polyacrylonitrile (PAN)/dimethylformamide (DMF)/$TiCl_4$. The influence of the pyrolysis temperature and holding time on the morphological characteristics, particle sizes and surface area of the prepared catalyst was investigated. The prepared catalysts were characterized by several analytical methods: high resolution scanning electron microscopy (HRSEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS). The XRD patterns showed that the supported $TiO_2$ nanocrystals are typically anatase, polycrystalline and body-centered tetragonal in structure. The EDS and XPS results complemented one another and confirmed the presence of carbon species in or on the $TiO_2$ layer, and the XPS data suggested the substitution of titanium in $TiO_2$ by carbon. Instead of using calcination, PAN pyrolysis was used to control the carbon content, and the mesoporosity was tailored by the applied temperature. The supported $TiO_2$ nanocrystals prepared by pyrolysis at 300, 350, and $400^{\circ}C$ for 3 h on a stainless steel mesh were actual supported carbon doped $TiO_2$ nanocrystals. Thus, $PAN/DMF/TiCl_4$ offers a facile, robust sol-gel related route for preparing supported carbon doped $TiO_2$ nanocomposites.

Surface Protection Obtained by Anodic Oxidation of New Ti-Ta-Zr Alloy

  • Vasilescu, C.;Drob, S.I.;Calderon Moreno, J.M.;Drob, P.;Popa, M.;Vasilescu, E.
    • Corrosion Science and Technology
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    • v.17 no.2
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    • pp.45-53
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    • 2018
  • A new 80Ti-15Ta-5Zr wt% alloy surface was protected by anodic oxidation in phosphoric acid solution. The protective oxide layer (TiO2, ZrO2 and Ta suboxides and thickness of 15.5 nm) incorporated $PO{_4}^{3-}$ ions from the solution, according to high resolution XPS spectra. The AFM analysis determined a high roughness with SEM detected pores (20 - 50 nm). The electrochemical studies of bare and anodically oxidized Ti-15Ta-5Zr alloy in Carter-Brugirard saliva of different pH values and saliva with 0.05M NaF, pointed to a nobler surface for the protected alloy, with a thicker electrodeposited oxide layer acting as a barrier against aggressive ions. The oxidized alloy significantly decreased corrosion current densities and total quantity of ions released into the oral environment in comparison with the bare one, at higher polarisation resistance and protective capacity of the electrodeposited layer. The impedance data revealed a bi-layered oxidation film formed by: a dense, compact, barrier layer in contact with the metallic substrate, decreasing the potential gradient across the metal/oxide layer/solution interface, reducing the anodic dissolution and a more permissive, porous layer in contact with the electrolyte. The open circuit potential for protected alloy shifted to nobler values, with thickening of the oxidation film signifying long-term protection.

Evaluation of the Microbiological Status of Raw Beef in Korea: Considering the Suitability of Aerobic Plate Count Guidelines

  • Kim, Hye-Jin;Kim, Dongwook;Kim, Hee-Jin;Song, Sung-Ok;Song, Young-Han;Jang, Aera
    • Food Science of Animal Resources
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    • v.38 no.1
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    • pp.43-51
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    • 2018
  • This study was conducted to analyze the microbiological contamination status of raw beef distributed in Korea, and evaluate the suitability of current aerobic plate count (APC) guidelines. We analyzed five years (2010-2014) of microbiological monitoring data obtained from the Ministry of Food and Drug Safety and investigated the microbiological status of raw beef collected from meat packing centers and meat shops in the Seoul/Gyeonggi, Gangwon, and Chungcheong regions in August 2015. From 2010-2014, most raw beef (>94%) displayed APC levels of < $1.0{\times}10^6CFU/g$. However, raw beef samples collected from all three regions in August 2015 had comparatively higher APC levels than those reported in previous years. To evaluate the relationship between the APC level and quality, changes in beef loin were evaluated during cold storage for 15 days at $4^{\circ}C$. On day 11, the mean APC level ($4.7{\times}10^6CFU/g$) conformed to current guidelines in Korea ($1.0{\times}10^7CFU/g$) and the pH value was 5.82. However, the sensory evaluation score for color and overall acceptability was under 3.0, meaning that the beef loin was not acceptable for eating. These results suggest that current APC guideline for raw beef should be lowered to $1.0{\times}10^6CFU/g$ to improve both the microbiological safety and palatability of raw beef.

Microbial Communities and Physicochemical Properties of Myeolchi Jeotgal (Anchovy Jeotgal) Prepared with Different Types of Salts

  • Shim, Jae Min;Lee, Kang Wook;Yao, Zhuang;Kim, Jeong A;Kim, Hyun-Jin;Kim, Jeong Hwan
    • Journal of Microbiology and Biotechnology
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    • v.27 no.10
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    • pp.1744-1752
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    • 2017
  • Myeolchi jeotgals (MJs) were prepared with purified salt (PS), solar salt aged for 1 year (SS), and bamboo salt (BS) melted 3 times at 10% and 20% (w/w) concentrations, and fermented for 28 weeks at $15^{\circ}C$. BS MJ showed higher pH and lower titratable acidities than the other samples because of the alkalinity of bamboo salt. Lactic acid bacteria counts increased until 4-6 weeks and then decreased gradually, and were not detected after 20 weeks from MJs with 10% salt. Yeast counts of PS MJs were higher than those of BS and SS MJs. Bacilli were detected in relatively higher numbers throughout the 28 weeks, like marine bacteria, but archae were detected in lower numbers during the first 10 weeks. When 16S rRNA genes were amplified from total DNA from PS MJ (10% salt) at 12 weeks, Tetragenococcus halophilus was the major species. However, Staphylococcus epidermidis was the dominant species for BS MJ at the same time point. In SS MJ, T. halophilus was the dominant species and S. epidermidis was the next dominant species. BS and SS MJs showed higher amino-type nitrogen, ammonia-type nitrogen, and volatile basic nitrogen contents than PS MJs. SS and BS were better than PS for the production of high-quality MJs.

Meat Quality and Storage Characteristics of Pork Loin Marinated in Grape Pomace

  • Lee, Hyun-Joo;Lee, Jae-Joon;Jung, Myung-Ok;Choi, Jung-Seok;Jung, Ji-Taek;Choi, Yang-Il;Lee, Jin-Kyu
    • Food Science of Animal Resources
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    • v.37 no.5
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    • pp.726-734
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    • 2017
  • This study investigated the meat quality and storage characteristics of pork loin marinated in grape pomace powder during different storage periods. The experimental design included six treatments : pork loin containing only 100% water (Control, C); pork loin containing a combination of 20% grape pomace and 80% water (T1); pork loin containing a combination of 40% grape pomace and 60% water (T2); pork loin containing a combination of 0.5% grape pomace powder and 95.5% water (T3); pork loin containing a combination of 1.0% grape pomace powder and 99.0% water (T4); and pork loin containing a combination of 2.0% grape pomace powder and 98.0% water (T5). The pork loins aged by grape pomace and grape pomace powder showed decreased crude protein, crude fat, crude ash, pH, redness, and yellowness values; however, their moisture, lightness, and shear force increased significantly. During cold storage, marination with grape pomace and grape pomace powder reduced the 2-thiobarbituric acid value, volatile basic nitrogen value, and total microbial count in pork loin. Thus, marination with grape pomace and grape pomace powder improved the meat quality and storage characteristics, and could be used to improve storage stability of pork loin.

Synthesis and Characterization of Red Organic Fluorescent of Perylene Bisimide Derivatives (Perylene Bisimide 유도체의 적색 유기 형광체 합성 및 특성 연구)

  • Lee, Seung Min;Jeong, Yeon Tae
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.30 no.9
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    • pp.577-582
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    • 2017
  • The white light of a hybrid LED is obtained by using red and green organic fluorescent layers made of polymethylmethacrylate (PMMA) films, which function as color down-conversion layers of blue light-emitting diodes. In this research, we studied the fluorescence properties of a red organic fluorophore, employing perylene bisimide derivatives applicable to hybrid LEDs. The solubility, thermal stability, and luminous efficiency are important characteristics of organic fluorophores for use in hybrid LEDs. The perylene fluorescent compounds (1A and 1B) were prepared by the reaction of 4-bromophenol and 4-iodophenol with N,N'-bis(4-bromo-2,6-diisopropylphenyl)-1, 6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxyl diimide (1) in the presence of dimethyl formaldehyde (DMF) at $70^{\circ}C$. The synthesized derivatives were characterized by using $^1H-NMR$, FT-IR, UV/Vis absorption and PL spectra, and TGA analysis. Compounds 1A and 1B showed absorption and emission at 570 nm and 604 nm in the UV/Vis spectrum. We also documented favorable solubility and thermal stability characteristics of the perylene fluorophores in our work. Perylene fluorophore 1, with the 4-bromophenol substituent 1A, exhibited particularly good thermal stability and solubility in organic solvents.

Calf Rearing Systems in Smallholder Dairy Farming Areas of Zimbabwe : A Diadnostic Study of the Nharira-Lancashire Area

  • Mandibaya, W.;Mutisi, C.;Hamudikuwanda, H.
    • Asian-Australasian Journal of Animal Sciences
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    • v.12 no.1
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    • pp.68-76
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    • 1999
  • A formal survey was carried out in Nharira-Lancashire areas located in Chivhu to assess the calf rearing systems practiced in smallholder dairy farming areas of Zimbabwe. A total of 47 farmers, collectively owning 305 cows and 194 calves of various breeds, participated in the survey. All the farmers allowed their calves to suckle their dams all day to obtain colostrum. The colostrums intake period was significantly (p < 0.05) shorter (5.2 vs 4.1 days) in the small scale commercial area (SSCA) compared to communal area (CA). Milk was first sold to the Nharira-Lancashire Milk Centre a day after the colostrum intake period ended. Most of the CA (91.3%) and SSCA (77.8%) farmers penned their cows and calves together at night during the colostrum intake period. Thereafter the calves were penned separate from their dams. After colostrum intake, two types of calf suckling systems were practised; twice a day suckling and twice a day then changed to once a day suckling. In both systems, suckling was allowed for 30 minutes after the cows had been hand milked. There was no significant (p < 0.05) difference in the mean weaning age of calves between the CA and SSCA (5.8 vs 5.4 months). The most common weaning method was through separation of the calves from the dams. The limitaitions to calf production in Chivhu were the prohibitively high costs of calf meals, poor feed resources during the dry season, a general lack of knowledge on calf rearing diseases and inappropriate calf housing.

Development of Bioelectric Impedance Measurement System Using Multi-Frequency Applying Method

  • Kim, J.H.;Jang, W.Y.;Kim, S.S.;Son, J.M.;Park, G.C.;Kim, Y.J.;Jeon, G.R.
    • Journal of Sensor Science and Technology
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    • v.23 no.6
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    • pp.368-376
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    • 2014
  • In order to measure the segmental impedance of the body, a bioelectrical impedance measurement system (BIMS) using multi-frequency applying method and two-electrode method was implemented in this study. The BIMS was composed of constant current source, automatic gain control, and multi-frequency generation units. Three experiments were performed using the BIMS and a commercial impedance analyzer (CIA). First, in order to evaluate the performance of the BIMS, four RC circuits connected with a resistor and capacitor in serial and/or parallel were composed. Bioelectrical impedance (BI) was measured by applying multi-frequencies -5, 10, 50, 100, 150, 200, 300, 400, and 500 KHz - to each circuit. BI values measured by the BIMS were in good agreement with those obtained by the CIA for four RC circuits. Second, after measuring BI at each frequency by applying multi-frequency to the left and right forearm and the popliteal region of the body, BI values measured by the BIMS were compared to those acquired by the CIA. Third, when the distance between electrodes was changed to 1, 3, 5, 7, 9, 11, 13, and 15 cm, BI by the BIMS was also compared to BI from the CIA. In addition, BI of extracellular fluid (ECF) was measured at each frequency ranging from 10 to 500 KHz. BI of intracellular fluid (ICF) was calculated by subtracting BI of ECF measured at 500 kHZ from BI measured at seven frequencies ranging from 50 to 500 KHz. BI of ICF and ECF decreased as the frequency increased. BI of ICF sharply decreased at frequencies above 300 KHz.