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Studies on the Semicarbazone Formation of Mono substituted Benzaldehydes (일치환 Bezaldehyde 의 Semicarbazone 생성 반응에 관한 연구)

  • Kim, Yong-In;Kim, Chang-Mean
    • Journal of the Korean Applied Science and Technology
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    • v.7 no.1
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    • pp.93-105
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    • 1990
  • Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

Purification and Characterization of a Fibrinolytic Enzyme Produced by Bacillus amyloliquefaciens HC188 (Bacillus amyloliquefaciens HC188이 생산하는 혈전분해 효소의 정제 및 특성)

  • Shin, So Hee;Hong, Sung Wook;Chung, Kun Sub
    • Microbiology and Biotechnology Letters
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    • v.41 no.1
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    • pp.33-43
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    • 2013
  • A bacterium producing a fibrinolytic enzyme was isolated from Cheonggukjang. The bacterium was identified as a strain of Bacillus amyloliquefaciens by 16S rDNA analysis and designated as B. amyloliquefaciens HC188. The optimum culture medium appeared to be one containing 0.5% (w/v) maltose and 0.5% (w/v) soytone. Bacterial growth in the optimal medium at $37^{\circ}C$ reached the stationary phase after 27 h of incubation and the fibrinolytic enzyme showed optimum activity at 24 h. The enzyme was purified by 20-80% ammonium sulfate precipitation, CM Sepharose fast flow ion exchange chromatography, and Sephacryl S-200HR column chromatography. Its specific activity was 38359.3 units/mg protein and the yield was 5.5% of the total activity of the crude extracts. The molecular weight was 24.7 kDa and the amino acids of the N-terminal sequence were AQSVPYGVSQIKAPA. The fibrinolytic enzyme activity had an optimum temperature of $40^{\circ}C$ and an optimum pH of 8.0, and the enzyme was stable in the ranges $20-40^{\circ}C$ and pH 6.0-8.0. Enzyme activity was increased by $Ca^{2+}$ and $Co^{2+}$ but inhibited by $Cu^{2+}$, EDTA, and PMSF. It is suggested that the purified enzyme is a metallo-serine protease.

Studies on Ammonium Adsorption by and Desorption from Various Soils -II. Desorption of Ammonium (토양별(土壤別) 암모늄의 흡착(吸着)및 탈착(脫着)에 관한 연구 -II. 암모늄의 탈착(脫着))

  • Shim, Sang-Chil;Park, Hoon;Kim, Moo-Sung;Kim, Kwang-Rai
    • Korean Journal of Soil Science and Fertilizer
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    • v.11 no.2
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    • pp.75-80
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    • 1979
  • Ammonium desorption from 16 soils treated with $(NH_4)_2HPO_4$ solution (2000 ppm $NH_4$) was investigated by seven extractions with 0.01M $CaCl_2$. 1. There were 2 to 4 steps alternately appeared with fast and slow mode. 2. Desorption equation, log y=b-ax where y is desorption amount, b a constant indicating adsorption maximum, a retention constant, and x extraction number, was held for each step. 3. Desorption rate (100${\times}$desorption / adsorption) was 65% for the average of 15 soils, maximum 87% in Gimcheon series, minimum 32% in Samgag series. Yongho series (a peat soil) showed 156% indicating the release of large quantity of indigenous soil ammonium. 4. Desorption rate was negatively correlated with initial adsorption and in this relation the tested soils were classified into 3 groups. 5. The cumulative desorption curve was approaching almost to maximum in all tested soils with seven extractions. The final retention amount, ranged from 25% of CEC (Gimhae series) to 502% (Samgag Series). 6. Amount and rate of desorption did not have any significant relation with Langmuir adsorption maxima of ammonium, CEC and contents of clay, available phosphorus and organic matter. 7. The above results may indicate that adsorption and desorption of ammonium is closely related with iron, aluminum silicate and adsorption and desorption characteristics of accompanied anions.

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Geographical origin discrimination of Korean variety, Angelica gigas Nakai by using TDU (Thermal Desorption Unit)-GC/MS (TDU-GC/MS를 이용한 한국품종 참당귀 국산 판별 기법)

  • Lee, Mi-Na;Kim, Yoon-Suk;Kim, Won-Il;Kim, Jeong-Gyu;Kwon, Oh-Kyung
    • Journal of Applied Biological Chemistry
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    • v.63 no.1
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    • pp.29-33
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    • 2020
  • The objective of this study was to develop a fast and accurate method of variety discrimination and geographical discrimination origin of Korean angelica (Korean variety, Angelica gigas Nakai) by using TDU-GC/MS. Two peaks of decursin and decursinol, which are coumarin derivatives were identified in the range of Total Ion Chromatogram (TIC) RT 26.9-27.2 of the Korean angelica by GC/MS analysis at the time of condensation in a refrigerated condensation system after thermal desorption of sample extracts. In case of Chinese angelica (Chinese variety), ligustilide peak was detected at the RT 17.2. In order to investigate the difference of volatile components according to the geographical origin of Korean variety, the mass spectra were measured by TDU-GC/MS at the range of m/z 40-400 amu. The TIC of domestic cultivation and Chinese cultivation of the Korean variety, Angelica gigas Nakai showed the same tendency as a whole. However, in partial scans of TIC, two peaks detected at 15.54 and 16.05 of RT showed different peak patterns between Korean angelica (Korean variety) cultivated in Korea and in China. The ratio of Peak A (RT 15.54) and B (RT 16.05) was 0.0-0.2 for domestic cultivation and 0.5-2.8 for Chinese cultivation, confirming the possibility of discriminating origin by comparing the TIC peak pattern of TDU-GC/MS.

Study on Characteristics of Corrosion Products Generated in Iron Artifacts after Conservation Treatments (보존처리 후 철제유물에 생성된 부식물 특성 연구)

  • Jeong, Ji-Hae;Yang, Hee-Jae;Ha, Jin-Uk
    • Journal of Conservation Science
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    • v.29 no.4
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    • pp.297-309
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    • 2013
  • Iron objects become corroded at fast speed from the moment when they are excavated, so it is needed to control corrosion through processes of conservation treatment. However, re-corrosion mostly takes place in excavate iron objects, although they have already gone through the process of conservation treatment, and it is more difficult to carry out the second conservation treatment of re-corroded excavated iron objects than the first conservation treatment, and it requires a longer period of time to treat them as well. In this study, aims to discover factors of re-corrosion by scientifically analyzing corrosion products generated during the process of storage after the process of conservation treatment. The finished on conservation treatment of the iron artifacts, which were unearthed from three ancient site in Gyeongju by using the same conservation method between 2002 and 2009, re-corrosion condition observed on the packaging-iron artifacts. Focused on 9 target forged iron artifacts among them, this study analyzed the physical changes by mass measurement, naked-eye and microscopic observations and the chemical changes by SEM-EDS, XRD, IC and ICP analysis. The results show that the yellowish brown corrosion products formed on the facing surface of part dropped from the artifacts had different associated forms but acicular shape. In addition, the acicular shape became clearer as the color changed from red to yellowish brown. According to the process when the conservation treatment was completed, the mass of the artifacts increased in proportion to the corrosion products and the chloride ion ($Cl^-$) concentration had a tendency to increase relatively. ${\beta}$-FeOOH (akaganeite) was confirmed in the XRD analysis for the corrosion products of all the collected samples. As a result of ICP analysis, $Na^+$ and $Ca^{2+}$ components were confirmed.

Synthesis of MnO2 Nanowires by Hydrothermal Method and their Electrochemical Characteristics (수열합성법을 이용한 망간 나노와이어 제조 및 이의 전기화학적 특성 연구)

  • Hong, Seok Bok;Kang, On Yu;Hwang, Sung Yeon;Heo, Young Min;Kim, Jung Won;Choi, Bong Gill
    • Applied Chemistry for Engineering
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    • v.27 no.6
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    • pp.653-658
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    • 2016
  • In this work, we developed a synthetic method for preparing one-dimensional $MnO_2$ nanowires through a hydrothermal method using a mixture of $KMnO_4$ and $MnSO_4$ precursors. As-prepared $MnO_2$ nanowires had a high surface area and porous structure, which are beneficial to the fast electron and ion transfer during electrochemical reaction. The microstructure and chemical structure of $MnO_2$ nanowires were characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller measurements. The electrochemical properties of $MnO_2$ nanowire electrodes were also investigated using cyclic voltammetry and galvanostatic charge-discharge with a three-electrode system. $MnO_2$ nanowire electrodes showed a high specific capacitance of 129 F/g, a high rate capability of 61% retention, and an excellent cycle life of 100% during 1000 cycles.

Performance Evaluation of Hazardous Substances using Measurement Vehicle of Field Mode through Emergency Response of Chemical Incidents

  • Lee, Yeon-Hee;Hwang, Seung-Ryul;Kim, Jae-Young;Kim, Kyun;Kwak, Ji Hyun;Kim, Min Sun;Park, Joong Don;Jeon, Junho;Kim, Ki Joon;Lee, Jin Hwan
    • Korean Journal of Environmental Agriculture
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    • v.34 no.4
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    • pp.294-302
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    • 2015
  • BACKGROUND: Chemical accidents have increased owing to chemical usage, human error and technical failures during the last decades. Many countries have organized supervisory authorities in charge of enforcing related rules and regulations to prevent chemical accidents. A very important part in chemical accidents has been coping with comprehensive first aid tool. Therefore, the present research has provided information with the initial applications concern to the rapid analysis of hazardous material using instruments in vehicle of field mode after chemical accidents. METHODS AND RESULTS: Mobile measurement vehicle was manufactured to obtain information regarding field assessments of chemical accidents. This vehicle was equipped with four instruments including gas chromatography with mass spectrometry (GC/MS), Fourier Transform Infrared Spectroscopy (FT-IR), Ion Chromatography (IC), and UV/Vis spectrometer (UV) to analyses of accident preparedness substances, volatile compounds, and organic gases. Moreover, this work was the first examined the evaluation of applicability for analysis instruments using 20 chemicals in various accident preparedness substances (GC/MS; 6 chemicals, FT-IR; 2 chemicals, IC; 11 chemicals, and UV; 1 chemical) and their calibration curves were obtained with high linearity ( r 2 > 0.991). Our results were observed the advantage of the high chromatographic peak capacity, fast analysis, and good sensitivity as well as resolution. CONCLUSION: When chemical accidents are occurred, the posted measurement vehicle may be utilized as tool an effective for qualitative and quantitative information in the scene of an accident owing to the rapid analysis of hazardous material.

Eritadenin Contents Analysis in Various Strains of Lentinula edodes using LC-MS/MS (LC-MS/MS를 이용한 표고 균주별 에리타데닌 함량 분석)

  • Park, Young-Ae;Lee, Kyoung-Tae;Bak, Won-Chull;Kim, Myung-Kil;Ka, Kang-Hyeon;Koo, Chung-Duck
    • The Korean Journal of Mycology
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    • v.39 no.3
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    • pp.239-242
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    • 2011
  • Eritadenine, a potent compound of hypocholesterolemic activity, was investigated in relation to its content in domestic cultivars and wild types of shiitake (Lentinula edodes). Eighteens strains of shiitake were tested for the quantification of eritadenine by LC-MS/MS analysis. Among the strains, wild type-40 was highest as the content was 3.912 mg/g. Also, Soohyangko was 3.352mg/g, Sanlim No. 9 3.008mg/g, Chunbaegko 2.832 mg/g, Gaeulhyang and KFRI 675 both 2.792 mg/g as high-content strains. Soohyangko and Chunbaegko are applied strains for registration in 2010. Soohyangko is high-temperature type with concentrated fruiting, and 90% of production occurs in the first year, thus, recovery of cost is very fast. Chunbaegko is mid-temperature type with concentrated flushing, and produces "hwago", the best quality, in spring. Wild type-40 is excellent in productivity and is prepared for registration. Wild type-40 could be used as parent strain to make new strain with high eritadenine content.

Fouling Study with Binary Protein Mixtures in Microfilration (이성분계 단백질 혼합물의 미세막 분리공정에서 막오염에 관한 연구)

  • Ahn, Byung Hun;Moon, Dong Ju;Yoo, Kye Sang;Ho, Chia Chi
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.236-242
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    • 2005
  • Membrane fouling by protein mixtures during microfiltration has been investigated for binary mixtures of bovine serum albumin (BSA), casein, lysozyme, pepsin, and ovalbumin. Filtration experiments were carried out using $0.2{\mu}m$ polycarbonate track-etched (PCTE) membrane in a stirred cell under constant transmembrane pressure (14 kPa) and concentration of hydrogen ion (pH=11) to study the effect of mixture composition on filtrate flux decline. Flux decline data were analyzed using a pore blockage-cake formation model developed recently. It was found that the model is in a good agreement with the experimental data. Fouling parameters such as the rate of pore blockage(${\alpha}$), the initial resistance of the protein deposit ($R_{po}$) and the increasing rate of the protein layer resistance(${\beta}$) were used to evaluate the rate of filtrate flow by membrane fouling in the binary mixture system. Generally, the trend of ${\alpha}$ is comparable with that of filtrate flux decline. It was also found that fast flux decreasing was observed over the binary mixture containing casein. The result is due to high value of the initial resistance of the protein deposit ($R_{po}$) over casein.

Problem Analysis and Improvement of an Experiment on Reactivityof Metals in ChemistryⅠ (화학Ⅰ 금속의 반응성 실험의 문제점 분석 및 개선방안)

  • Seong, Suk-kyoung;Choi, Chui-Im;Jeong, Dae-Hong
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.368-376
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    • 2009
  • In this study we investigated and tried to understand problems monitored in an experiment on reactivity of metals in chemistry I. Three problems were discussed. First, the reason that aluminium plate does not react with other metal ions such as zinc, iron and copper was studied and the way to overcome this problem was suggested. Second, the reason that the bubbles were generated when FeS$O_4$(aq) and Zn(s) react was discussed. Third, the precipitates which appeared in the reaction of FeS$O_4$(aq) and Zn(s) were identified. Through reference study and experimental investigation, we could reach the following results. First, aluminium could not react with other metal ions due to the surface oxide layer that is formed very fast and prevents aluminium from reacting with metal ions in solution. This problem could be overcome by allowing a competing reaction of acid and aluminium during the reaction of aluminium and metal ions. Second, the observed bubbles were identified to be hydrogen gas, produced by the reaction between metals and hydronium ion in the solution. Third, black precipitates that were produced on the surface of zinc plate and exhibited magnetic property were characterized to be $Fe_3O_4$(s), and brown precipitates that were produced in the solution phase were to be $Fe_2O_3$(s) by the analysis of X-ray photoelectron spectra.