• Title/Summary/Keyword: Chemical bond

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Experimental Studies on the Properties of Epoxy Resin Mortars (에폭시 수지 모르터의 특성에 관한 실험적 연구)

  • 연규석;강신업
    • Magazine of the Korean Society of Agricultural Engineers
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    • v.26 no.1
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    • pp.52-72
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    • 1984
  • This study was performed to obtain the basic data which can be applied to the use of epoxy resin mortars. The data was based on the properties of epoxy resin mortars depending upon various mixing ratios to compare those of cement mortar. The resin which was used at this experiment was Epi-Bis type epoxy resin which is extensively being used as concrete structures. In the case of epoxy resin mortar, mixing ratios of resin to fine aggregate were 1: 2, 1: 4, 1: 6, 1: 8, 1:10, 1 :12 and 1:14, but the ratio of cement to fine aggregate in cement mortar was 1 : 2.5. The results obtained are summarized as follows; 1.When the mixing ratio was 1: 6, the highest density was 2.01 g/cm$^3$, being lower than 2.13 g/cm$^3$ of that of cement mortar. 2.According to the water absorption and water permeability test, the watertightness was shown very high at the mixing ratios of 1: 2, 1: 4 and 1: 6. But then the mixing ratio was less than 1 : 6, the watertightness considerably decreased. By this result, it was regarded that optimum mixing ratio of epoxy resin mortar for watertight structures should be richer mixing ratio than 1: 6. 3.The hardening shrinkage was large as the mixing ratio became leaner, but the values were remarkably small as compared with cement mortar. And the influence of dryness and moisture was exerted little at richer mixing ratio than 1: 6, but its effect was obvious at the lean mixing ratio, 1: 8, 1:10,1:12 and 1:14. It was confirmed that the optimum mixing ratio for concrete structures which would be influenced by the repeated dryness and moisture should be rich mixing ratio higher than 1: 6. 4.The compressive, bending and splitting tensile strenghs were observed very high, even the value at the mixing ratio of 1:14 was higher than that of cement mortar. It showed that epoxy resin mortar especially was to have high strength in bending and splitting tensile strength. Also, the initial strength within 24 hours gave rise to high value. Thus it was clear that epoxy resin was rapid hardening material. The multiple regression equations of strength were computed depending on a function of mixing ratios and curing times. 5.The elastic moduli derived from the compressive stress-strain curve were slightly smaller than the value of cement mortar, and the toughness of epoxy resin mortar was larger than that of cement mortar. 6.The impact resistance was strong compared with cement mortar at all mixing ratios. Especially, bending impact strength by the square pillar specimens was higher than the impact resistance of flat specimens or cylinderic specimens. 7.The Brinell hardness was relatively larger than that of cement mortar, but it gradually decreased with the decline of mixing ratio, and Brinell hardness at mixing ratio of 1 :14 was much the same as cement mortar. 8.The abrasion rate of epoxy resin mortar at all mixing ratio, when Losangeles abation testing machine revolved 500 times, was very low. Even mixing ratio of 1 :14 was no more than 31.41%, which was less than critical abrasion rate 40% of coarse aggregate for cement concrete. Consequently, the abrasion rate of epoxy resin mortar was superior to cement mortar, and the relation between abrasion rate and Brinell hardness was highly significant as exponential curve. 9.The highest bond strength of epoxy resin mortar was 12.9 kg/cm$^2$ at the mixing ratio of 1:2. The failure of bonded flat steel specimens occurred on the part of epoxy resin mortar at the mixing ratio of 1: 2 and 1: 4, and that of bonded cement concrete specimens was fond on the part of combained concrete at the mixing ratio of 1 : 2 ,1: 4 and 1: 6. It was confirmed that the optimum mixing ratio for bonding of steel plate, and of cement concrete should be rich mixing ratio above 1 : 4 and 1 : 6 respectively. 10.The variations of color tone by heating began to take place at about 60˚C, and the ultimate change occurred at 120˚C. The compressive, bending and splitting tensile strengths increased with rising temperature up to 80˚ C, but these rapidly decreased when temperature was above 800 C. Accordingly, it was evident that the resistance temperature of epoxy resin mortar was about 80˚C which was generally considered lower than that of the other concrete materials. But it is likely that there is no problem in epoxy resin mortar when used for unnecessary materials of high temperature resistance. The multiple regression equations of strength were computed depending on a function of mixing ratios and heating temperatures. 11.The susceptibility to chemical attack of cement mortar was easily affected by inorganic and organic acid. and that of epoxy resin mortar with mixing ratio of 1: 4 was of great resistance. On the other hand, when mixing ratio was lower than 1 : 8 epoxy resin mortar had very poor resistance, especially being poor resistant to organicacid. Therefore, for the structures requiring chemical resistance optimum mixing of epoxy resin mortar should be rich mixing ratio higher than 1: 4.

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The Crystal and Molecular Structure of 25,26,27,28-Tetrnacetoxy[4]Arene${\cdot}$Monohydrate (25,26,27,28-테트라아세트오키시[4]에렌${\cdot}$일수화물의 결정 및 분자구조)

  • Choong Tai Ahn;Kwanghyun No
    • Journal of the Korean Chemical Society
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    • v.37 no.3
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    • pp.344-350
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    • 1993
  • 25,26,27,28-Tetraacetoxycalix[4]arene·monohydrate is orthorhombic, space group Pbca with a = 14.979(4), b = 15.154(4), c = 27.890(3) ${\AA}$, Z = 8, V = 6330.6 ${\AA}^{-3}$, D$_c$ = 1.28 $g{\cdot}cm^{-3}$, (Mo K${\alpha}$) = 0.71069 ${\AA}$, ${\mu}$ = 0.86 cm$^{-1}$, F(000) = 2600, and R = 0.069 for 3376 unique observed reflections with I > 1.0 ${\sigma}$(I). The structure was solved by direct methods and refined by cascade diagonal least-squares refinement. All the C-H bond lengths(= 0.96 ${\AA}$), the methyl groups and the methylene groups are fixed and refined as the rigid groups with ideal geometry. The macrocycle exists in the 1,3 alternate conformation (by Conforth) making the angles of 110.7, 684, 113.7 and 68.8$^{\circ}$ between the benzene rings and the methylenic mean plane, and four each acetoxy groups are twisted away from their own benzene rings with the angles of 68.2, 97.6, 78.9 and 71.3$^{\circ}$, respectively. The relative dihedral angles between two opposite side of the benzene rings are 135.6$^{\circ}$ for the rings (1) and (3) and 135.2$^{\circ}$ for (2) and (4). A water molecule which has nearly the same height of the methylenic plane of the macrocycle in the c-axis, is located within the distances of 2.942(5) ${\AA}$ from the O(8) atom of the carbonyl group and 2.901 ${\AA}$ from, another O(2)(1/2-x, -1/2+y, z). The shortest contact between the molecule is 3.193 ${\AA}$ from the O(4) to the C(3)(1/2+x, 1/2-y,-z).

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THE BOND CHARACTERISTICS OF PORCELAIN FUSED BY TITANIUM SURFACE MODIFICATION (타이타늄의 표면개질에 따른 도재 결합 특성)

  • Choi, Taek-Huw;Park, Sang-Won;Vang, Mong-Sook;Yang, Hong-So;Park, Ha-Ok;Lim, Hyun-Pil;Oh, Gye-Jeong;Kim, Hyun-Seung;Lee, Kwang-Min;Lee, Kyung-Ku
    • The Journal of Korean Academy of Prosthodontics
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    • v.45 no.2
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    • pp.169-181
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    • 2007
  • Statement of problem: Titanium is well known as a proper metal for the dental restorations, because it has an excellent biocompatibility, resistance to corrosion, and mechanical property. However, adhesion between titanium and dental porcelains is related to the diffusion of oxygen to the reaction layers formed on cast-titanium surfaces during porcelain firing and those oxidized layers make the adhesion difficult to be formed. Many studies using mechanical, chemical and physical methods to enhance the titanium-ceramic adhesion have been actively performed. Purpose: This study meant to comparatively analyse the adhesion characteristics depending on different titanium surface coatings after coating the casts and wrought titanium surfaces with Au and TiN. Material and method: In this study, the titanium specimens (CP-Ti, Grade 2, Kobe still Co. Japan) were categorized into cast and wrought titanium. The wrought titanium was cast by using the MgO-based investment(Selevest CB, Selec). The cast and wrought titanium were treated with Au coating($ParaOne^{(R)}$., Gold Ion Sputter, Model PS-1200) and TiN coating(ATEC system, Korea) and the ultra low fusing dental porcelain was fused and fired onto the samples. Biaxial flection test was done on the fired samples and the porcelain was separated. The adhesion characteristics of porcelain and titanium after firing and the specimen surfaces before and after the porcelain fracture test were observed with SEM. The atomic percent of Si on all sample surfaces was comparatively analysed by EDS. In addition, the constituents of specimen surface layers after the porcelain fracture and the formed compound were evaluated by X-ray diffraction diagnosis. Result: The results of this study were obtained as follows : 1. The surface characteristics of cast and wrought titanium after surface treatment(Au, TiN, $Al_2O_3$ sandblasting) were similar and each cast and wrought titanium showed similar bonding characteristics. 2. Before and after the biaxial flection test, the highest atomic weight change of Si component was found in $Al_2O_3$ sandblasted wrought titanium(28.6at.% $\rightarrow$ 8.3at.%). On the other hand, the least change was seen in Au-Pd-In alloy(24.5at.% $\rightarrow$ 9.1at.%). 3. Much amount of Si components was uniformly distributed in Au and TiN coated titanium, but less amount of Si's was unevenly dispersed on Al2O3 sandblasting surfaces. 4. In X-ray diffraction diagnosis after porcelain debonding, we could see $Au_2Ti$ compound and TiN coating layers on Au and TiN coated surfaces and $TiO_2$, typical oxide of titanium, on all titanium surfaces. 5. Debonding of porcelain on cast and wrought titanium surface after the biaxial flection is considered as a result of adhesion deterioration between coating layers and titanium surfaces. We found that there are both adhesive failure and cohesive failure at the same time. Conclusion: These results showed that the titanium-ceramic adhesion could be improved by coating cast and wrought titanium surfaces with Au and TiN when making porcelain fused to metal crowns. In order to use porcelain fused to titanium clinically, it is considered that coating technique to enhance the bonding strength between coating kKlayers and titanium surfaces should be developed first.

Electrochemical Properties of Pyrolytic Carbon and Boron-doped Carbon for Anode Materials In Li-ion Secondary Batteries (리튬 이온 이차전지 부극용 열분해 탄소 및 붕소첨가 탄소의 전기화학적 특성)

  • Kwon, Ik-Hyun;Song, Myoung-Youp;Bang, Eui-Yong;Han, Young-Soo;Kim, Ki-Tae;Lee, Jai-Young
    • Journal of the Korean Electrochemical Society
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    • v.5 no.1
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    • pp.30-38
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    • 2002
  • Disordered carbon and boron-substituted disordered carbons $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ were synthesized by Pyrolysis of LPG(liquid Propane gas)and $BCl_3$. Their electrochemical properties as anode materials for Li-ion secondary batteries were then investigated. When PVDF is added to the sample in a weight ratio 5 : 95, the disordered carbon with x=0.00 had the first discharge capacity 374 mAh/g. Its cycling performance was relatively good from the second cycle and it had the discharge capacity 258 mAh/g at the 10th cycle. When PVDF is added to the sample in a weight ratio 5 : 95, the sample with x=0.05 among the samples $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ exhibited the largest first discharge capacity 860 mAh/g and discharge capacity 181 mAh/g at the 10th cycle. All the samples had similar cycling performances from the second cycle. The sample $C_{0.90}B_{0.10}$ showed the best electrochemical properties as a anode materials fur Li-ion secondary battery from the view points of the first discharge capacity(853 mAh/g when $10w1.\%$ PVDF is used), cycling performance, discharge capacity(400mAh/g at the 10th cycle when $10wt.\%$ PVDF is used). All the samples showed generally larger charge and discharge capacities when $10wt.\%$ PVDF ratter than $5wt.\%$ PVDF is used. The plateau region in the range of voltage lower than 1.25V becomes larger probably since the structure becomes less disordered by the addition of boron. When boron is added, the charge and discharge capacities decreased suddenly at the second cycle. This may be become only a part of Li are reversibly deintercalated and intercalated and a part of Li which are strongly combined with B are not deintercalated. The increases in charge and discharge capacities are considered to be resulted from the increase in the potential of Li in the boron-added carbons, caused by the strengthening of the chemical bond between the intercalated Li and the boron-carbon host since the boron acts as electron acceptor.

Optical Properties of SiNx Thin Films Grown by PECVD at 200℃ (200℃의 저온에서 PECVD 기법으로 성장한 SiNx 박막의 열처리에 따른 광학적 특성 변화 규명)

  • Lee, Kyung-Su;Kim, Eun-Kyeom;Son, Dae-Ho;Kim, Jeong-Ho;Yim, Tae-Kyung;An, Seung-Man;Park, Kyoung-Wan
    • Journal of the Korean Vacuum Society
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    • v.20 no.1
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    • pp.42-49
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    • 2011
  • We deposited $SiN_x$ thin films by using PECVD technique at $200^{\circ}C$ with various flow ratios of the $SiH_4/N_2$ gases. The photoluminescence measurements revealed that the maximum emission wavelength shifted to long wavelength as the ratio increased, however, positions of the several peak wavelengths, such as 1.9, 2.2, 2.4, and 3.1 eV, were independent on the ratio. Changes of the photoluminescence spectra were measured in the $N_{2}-$, $H_{2}-$, and $O_2$-annealed films. The luminescence intensities increased after the annealing process. In particular, the maximum emission wavelength shifted to short wavelength after $H_{2}-$ or $O_2$-annealing. But there were still several peaks on the spectra of all annealed films, several peak positions remained to be unchanged after the annealing. As for the light emission mechanism, we have considered the defect states of the Si- and N- dangling bonds in the $SiN_x$ energy gap, so that the energy transitions from/to the conduction/valence bands and the defect states in the gap were attributed to the light emission in the $SiN_x$ films. The experimental results point to the possibility of a Si-based light emission materials for flexible Si-based electro-optic devices.

유청단백질로 만들어진 식품포장재에 관한 연구

  • Kim, Seong-Ju
    • 한국유가공학회:학술대회논문집
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    • 2002.04a
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    • pp.59-60
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    • 2002
  • Edible films such as wax coatings, sugar and chocolate covers, and sausage casings, have been used in food applications for years$^{(1)}$ However, interest in edible films and biodegradable polymers has been renewed due to concerns about the environment, a need to reduce the quantity of disposable packaging, and demand by the consumer for higher quality food products. Edible films can function as secondary packaging materials to enhance food quality and reduce the amount of traditional packaging needed. For example, edible films can serve to enhance food quality by acting as moisture and gas barriers, thus, providing protection to a food product after the primary packaging is opened. Edible films are not meant to replace synthetic packaging materials; instead, they provide the potential as food packagings where traditional synthetic or biodegradable plastics cannot function. For instance, edible films can be used as convenient soluble pouches containing single-servings for products such as instant noodles and soup/seasoning combination. In the food industry, they can be used as ingredient delivery systems for delivering pre-measured ingredients during processing. Edible films also can provide the food processors with a variety of new opportunities for product development and processing. Depends on materials of edible films, they also can be sources of nutritional supplements. Especially, whey proteins have excellent amino acid balance while some edible films resources lack adequate amount of certain amino acids, for example, soy protein is low in methionine and wheat flour is low in lysine$^{(2)}$. Whey proteins have a surplus of the essential amino acid lysine, threonine, methionine and isoleucine. Thus, the idea of using whey protein-based films to individually pack cereal products, which often deficient in these amino acids, become very attractive$^{(3)}$. Whey is a by-product of cheese manufacturing and much of annual production is not utilized$^{(4)}$. Development of edible films from whey protein is one of the ways to recover whey from dairy industry waste. Whey proteins as raw materials of film production can be obtained at inexpensive cost. I hypothesize that it is possible to make whey protein-based edible films with improved moisture barrier properties without significantly altering other properties by producing whey protein/lipid emulsion films and these films will be suitable far food applications. The fellowing are the specific otjectives of this research: 1. Develop whey protein/lipid emulsion edible films and determine their microstructures, barrier (moisture and oxygen) and mechanical (tensile strength and elongation) properties. 2. Study the nature of interactions involved in the formation and stability of the films. 3. Investigate thermal properties, heat sealability, and sealing properties of the films. 4. Demonstrate suitability of their application in foods as packaging materials. Methodologies were developed to produce edible films from whey protein isolate (WPI) and concentrate (WPC), and film-forming procedure was optimized. Lipids, butter fat (BF) and candelilla wax (CW), were added into film-forming solutions to produce whey protein/lipid emulsion edible films. Significant reduction in water vapor and oxygen permeabilities of the films could be achieved upon addition of BF and CW. Mechanical properties were also influenced by the lipid type. Microstructures of the films accounted for the differences in their barrier and mechanical properties. Studies with bond-dissociating agents indicated that disulfide and hydrogen bonds, cooperatively, were the primary forces involved in the formation and stability of whey protein/lipid emulsion films. Contribution of hydrophobic interactions was secondary. Thermal properties of the films were studied using differential scanning calorimetry, and the results were used to optimize heat-sealing conditions for the films. Electron spectroscopy for chemical analysis (ESCA) was used to study the nature of the interfacial interaction of sealed films. All films were heat sealable and showed good seal strengths while the plasticizer type influenced optimum heat-sealing temperatures of the films, 130$^{\circ}$C for sorbitol-plasticized WPI films and 110$^{\circ}$C for glycerol-plasticized WPI films. ESCA spectra showed that the main interactions responsible for the heat-sealed joint of whey protein-based edible films were hydrogen bonds and covalent bonds involving C-0-H and N-C components. Finally, solubility in water, moisture contents, moisture sorption isotherms and sensory attributes (using a trained sensory panel) of the films were determined. Solubility was influenced primarily by the plasticizer in the films, and the higher the plasticizer content, the greater was the solubility of the films in water. Moisture contents of the films showed a strong relationship with moisture sorption isotherm properties of the films. Lower moisture content of the films resulted in lower equilibrium moisture contents at all aw levels. Sensory evaluation of the films revealed that no distinctive odor existed in WPI films. All films tested showed slight sweetness and adhesiveness. Films with lipids were scored as being opaque while films without lipids were scored to be clear. Whey protein/lipid emulsion edible films may be suitable for packaging of powder mix and should be suitable for packaging of non-hygroscopic foods$^{(5,6,7,8,)}$.

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Miscibility and Specific Intermolecular Interaction Strength of PBI/PI Blends Depending on Polyimide Structure(II) - Blend Systems with PIs Synthesized by DSDA - (폴리이미드 구조변화에 의한 방향족 PBI/PI 블렌드의 상용성 및 상호작용의 세기(II) - DSDA로 합성한 PI들과의 블랜드들 -)

  • Ahn, Tae-Kwang
    • Applied Chemistry for Engineering
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    • v.9 no.2
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    • pp.207-213
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    • 1998
  • On the basis of the previous study[1], miscibility were investigated and intermolecular interaction strength for the miscibility were relatively compared for the blends poly{2,2-(m-phenylene)-5,5'-bibenzimidazole}(PBI) with two aromatic polyimides (PIs) synthesized by another dianhydride. Aromatic PAAs were prepared by the reaction of condensation of two diamines, 4,4'-methylene dianiline(4,4'-MDA) and 4,4'-oxydianiline(4,4'-ODA) with 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride(DSDA) using DMAc, and then converted into PIs after curing. PBI/PAA blends were prepared by solution blending. Cast films or precipitated powders of the PBI/PAA blends were cared at a high temperature to transform into PBI/PIs blends. Miscibility and specific intermolecular interaction for miscibility in the blends were investigated, and compared with previous polyimide structures of PBI/PIs blends [1]. Two blends, PBI/DSDA+4,4'-MDA(Blend-V) and PBI/DSDA+4,4'-ODA(Blend-VI), were found miscible : the evidences were optically clear films, synergistic single composition dependent $T_g{\prime}s$, and frequency shifts of N-H stretching band as much as $39{\sim}40cm^{-1}$, and of C=O stretching band near 1730 and $1780cm^{-1}$, 5~6 and $3{\sim}4cm^{-1}$, respectively. The specific intermolecular interactions existing between PBI and PIs were relatively analyzed with the area(A) formed between the $T_g{\prime}s$ of the measured and that of the calculated by the Fox equation at all compositions, the ${\kappa}$ values in Gordon-Taylor equation obtained from the measured $T_g{\prime}s$, and differences of the frequency shifts in the functional N-H and carbonyl stretching band. From the results, the area(A) and the ${\kappa}$ values for Blend-V and VI were smaller than those for Blend-III and IV used in previous study[1]. Differences of the frequency shifts in the functional groups(N-H and C=O) also showed similar tendency. Thus, specific intermolecular interaction strength in terms of hydrogen bonding of PBI/PI blends is dependent upon chemical structures of PIs, that is, PIs it seems that $SO_2$ group in dianhydride(DSDA) has weaker hydrogen bond strength than those of C=O in BTDA. In other words, it implies that the former occupied bulk space than the latter due to the sterric effect.

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Improving Curing Rate and Physical Properties of Korean Dendropanax Lacquer with Thermal and Photo Initiator by Dual Curing (이중경화법을 이용한 열개시제 및 광개시제가 배합된 황칠도료의 경화속도 촉진 및 물성향상 연구)

  • Hwang, Hyeon-Deuk;Moon, Je-Ik;Park, Cho-Hee;Kim, Hyun-Joong;Hwang, Baik
    • Journal of the Korean Wood Science and Technology
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    • v.38 no.4
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    • pp.333-340
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    • 2010
  • The Korean Dendropanax lacquer, made from a natural resinous sap from Dendropanax orbifera Lev., was used as a golden and transparent varnish for the traditional artifacts (armor uits, helmets, arrowheads, etc.) to make them be brilliant golden color. The cured film of the acquer has excellent protective properties such as weatherability, water resistance, and nticorrosive. But, one of disadvantages is that takes a long time and much energy to fulfill curing the lacquer. The chemical constituents of the lacquer contained conjugated diene compounds s the photopolymerizable monomers. These monomers easily polymerized in sunlight to form olden-colored, hard-coating films in a short time. Photooxidation may be one of the most mportant reactions in the chemistry of the lacquer. Although the Korean Dendropanax Lacquer hould be dried to a thoroughly dry stage to achieve optimal film properties, curing with elevated emperatures may be required for the protracted curing time at atmospheric temperature. So we ntended to accelerate the curing rate of the lacquer by dual curing of thermal and radiation uring. The effect of thermal initiator on the thermal curing reaction was evaluated by monitoring he changes in double bond peak with FT-IR. Then the curing rate of the lacquer blended with hermal initiator and photoinitiator together was measured during dual curing using a RPT with V spot curing machine. Thermal initiator not only accelerated the curing rate but also improved he physical property. And the curing rate of the Korean Dendropanax lacquer was improved by ual curing method of thermal and UV curing. According to these results, the application area of he Korean Dendropanax lacquer could be expanded to surface coatings for electronic devices uch as mobile phones or electronics.

Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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Uranium Adsorption Properties and Mechanisms of the WRK Bentonite at Different pH Condition as a Buffer Material in the Deep Geological Repository for the Spent Nuclear Fuel (사용후핵연료 심지층 처분장의 완충재 소재인 WRK 벤토나이트의 pH 차이에 따른 우라늄 흡착 특성과 기작)

  • Yuna Oh;Daehyun Shin;Danu Kim;Soyoung Jeon;Seon-ok Kim;Minhee Lee
    • Economic and Environmental Geology
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    • v.56 no.5
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    • pp.603-618
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    • 2023
  • This study focused on evaluating the suitability of the WRK (waste repository Korea) bentonite as a buffer material in the SNF (spent nuclear fuel) repository. The U (uranium) adsorption/desorption characteristics and the adsorption mechanisms of the WRK bentonite were presented through various analyses, adsorption/desorption experiments, and kinetic adsorption modeling at various pH conditions. Mineralogical and structural analyses supported that the major mineral of the WRK bentonite is the Ca-montmorillonite having the great possibility for the U adsorption. From results of the U adsorption/desorption experiments (intial U concentration: 1 mg/L) for the WRK bentonite, despite the low ratio of the WRK bentonite/U (2 g/L), high U adsorption efficiency (>74%) and low U desorption rate (<14%) were acquired at pH 5, 6, 10, and 11 in solution, supporting that the WRK bentonite can be used as the buffer material preventing the U migration in the SNF repository. Relatively low U adsorption efficiency (<45%) for the WRK bentonite was acquired at pH 3 and 7 because the U exists as various species in solution depending on pH and thus its U adsorption mechanisms are different due to the U speciation. Based on experimental results and previous studies, the main U adsorption mechanisms of the WRK bentonite were understood in viewpoint of the chemical adsorption. At the acid conditions (<pH 3), the U is apt to adsorb as forms of UO22+, mainly due to the ionic bond with Si-O or Al-O(OH) present on the WRK bentonite rather than the ion exchange with Ca2+ among layers of the WRK bentonite, showing the relatively low U adsorption efficiency. At the alkaline conditions (>pH 7), the U could be adsorbed in the form of anionic U-hydroxy complexes (UO2(OH)3-, UO2(OH)42-, (UO2)3(OH)7-, etc.), mainly by bonding with oxygen (O-) from Si-O or Al-O(OH) on the WRK bentonite or by co-precipitation in the form of hydroxide, showing the high U adsorption. At pH 7, the relatively low U adsorption efficiency (42%) was acquired in this study and it was due to the existence of the U-carbonates in solution, having relatively high solubility than other U species. The U adsorption efficiency of the WRK bentonite can be increased by maintaining a neutral or highly alkaline condition because of the formation of U-hydroxyl complexes rather than the uranyl ion (UO22+) in solution,and by restraining the formation of U-carbonate complexes in solution.