• Title/Summary/Keyword: DMA-DMA

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Nucleophilic Substitution Reactions of Thiopheneethyl Arenesulfonates with Anilines and N,N-Dimethylanilines

  • 오혁근;윤정환;조인호;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.390-394
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    • 1997
  • Nucleophilic substitution reactions of 2-thiopheneethyl benzenesulfonates (2-TEB) and 3-thiopheneethyl benzenesulfonates (3-TEB) with anilines and N,N-dimethylanilines (DMA) are investigated in acetonitrile at 60.0 ℃. The cross-interaction constants ρxz determined for the reactions with anilines are large negative (- 0.50) which are comparable to those for the similar predominantly frontside-attack SN2 reactions of 1-phenylethyl (1-PEB), 2-phenylethyl (2-PEB) and cumyl benzenesulfonates. A large negative ρxz value (- 0.4∼- 0.8) is considered to provide a mechanistic criterion for the frontside-attack SN2 mechanism with a four-center transition state. In agreement with this proposal the kinetic isotope effects, kH/kD, involving deuterated aniline nucleophiles are all greater than one reflecting partial N-H(D) bond cleavage in the transition state. The MO theoretical reactant structures of 1-PEB, 2-PEB and 2-TEB based on the PM3 calculation show that the benzene ring blocks the backside nucleophile approach to the reaction center carbon (Cα) enforcing the frontside-attack SN2 mechanism.

Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile

  • 이해황;이지원;고한중;이익천
    • Bulletin of the Korean Chemical Society
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    • v.19 no.6
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    • pp.642-645
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    • 1998
  • The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAS) in acetonitrile at -15.0 ℃ are investigated. The magnitude of ρx (= -2.8 ∼ -2.9) and ρy (= 0.9 ∼ 1.3, after correcting for the fall-off), and the negative sign of ρxy (= -0.12) for the reactions with anilines suggest an associative SN2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects $(k_H/k_D>1.0)$ involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.

Characterization of Healing Agent Candidates for Self-healing Applications (자가손상복구용 복구액의 특성 분석)

  • Liu, Xing;Lee, Jong-Keun;Kim, Jung-Seok
    • Proceedings of the KSR Conference
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    • 2008.11b
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    • pp.1668-1673
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    • 2008
  • 고분자 복합재 구조물의 경우 일반적으로 여러 층의 단층(laminar)이 적층된 구조로 이루어져 있으며, 모재균열, 층간분리 및 섬유파단과 같은 손상이 발생되어 파단에 이르게 된다. 자가손상 복구기법은 복합소재의 열경화성 수지 내에 손상복구액을 포함하고 있는 마이크로캡슐과 촉매를 투입하여 외부의 도움 없이 손상을 치료할 수 있는 방법으로, 소재의 디자인에 있어서 새로운 페러다임을 제공할 수 있는 것으로 현재 많은 연구가 진행되고 있다. 본 연구에서는 ENB(5-ethylidene-2-norbornene)와 DCPD(dicyclopentadiene)에 대하여 DMA(dynamic mechanical analysis)와 DSC(differential scanning calorimetry)를 이용하여 특성을 분석하였다. 또한 그들의 ROMP(ring-opening metathesis polymerization)반응과의 관계를 조사하였으며, ENB와 DCPD 블렌드에 대한 복구액으로서의 특성도 조사하였다. 본 연구실에서 합성된 두 가지 다른 종류의 ROMP 경화제에 대한 실제 자가손상복구에으로서의 적용상 특성도 연구하였다.

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Preparation and Characterization of Ophthalmic Hydrophilic Silicone Lens Containing Zinc Oxide and Iron Oxide Nanoparticles

  • Shin, Su-Mi;Sung, A-Young
    • Korean Journal of Materials Research
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    • v.31 no.8
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    • pp.427-432
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    • 2021
  • This study uses silicone monomer, DMA, crosslinking agent EGDMA, and initiator AIBN as a basic combination to prepare hydrogel lenses using fluorine-based perfluoro polyether and iron oxide and zinc oxide nanoparticles as additives. After manufacturing the lens using iron oxide nanoparticles and zinc oxide nanoparticles, the optical, physical properties, and polymerization stability are evaluated to investigate the possibility of application as a functional hydrogel lens material. As a result of this experiment, it is found that the addition of the wetting material containing fluorine changes the surface energy of the produced hydrogel lens, thereby improving the wettability. Also, the addition of iron oxide and zinc oxide nanoparticles satisfies the basic hydrogel ophthalmic lens properties and slightly increases the UV blocking performance; it also increases the tensile strength by improving the durability of the hydrogel lens. The polymerization stability of the nanoparticles evaluated through the eluate test is found to be excellent. Therefore, it is judged that these materials can be used in various conditions as high functional hydrogel lens material.

Static Dielectric Constant and Relaxation Time for the Binary Mixture of Water, Ethanol, N. N-Dimethylformamide, Dimethylsulphoxide, and N, M-Dimethylacetamide with 20Hethoxyethanol

  • Ajay Chaudgari;N. M. More;S. C. Mehrotra
    • Bulletin of the Korean Chemical Society
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    • v.22 no.4
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    • pp.357-361
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    • 2001
  • Frequency spectra of the complex permittivity of 2-methoxyethanol (2-ME) with water, ethanol, dimethylsulphoxide (DMSO), N,N-dimethylformamide (DMF) and N,N-dimethylacatamide (DMA) have been determined over the frequency range of 10 MHz to 20 GHz at 25 $^{\circ}C$, using the Time domain reflectometry method, for 11 concentrations for each system. The static dielectric constant, dielectric constant at microwave frequency, relaxation time, excess dielectric parameters, and Kirkwood correlation factor have been determined. The relaxation in these systems within the frequency range can be described by a single relaxation time constant, using the Debye model. The parameters show a systematic change with the concentration.

Preparation and Analysis of High Functional Silicone Hydrogel Lens Containing Metal Oxide Nanoparticles by Photopolymerizaion

  • Heo, Ji-Won;Sung, A-Young
    • Korean Journal of Materials Research
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    • v.32 no.4
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    • pp.193-199
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    • 2022
  • In this study, lenses are fabricated using various nanomaterials as additives to a silicone polymer made with an optimum mixing ratio and short polymerization time. In addition, PVP is added at a ratio of 1 % to investigate the physical properties according to the degree of dispersion, and the compatibility with hydrophobic silicone and the possibility of application as a functional lens material are confirmed. The main materials are SIU as a silicone monomer, DMA, a hydrophilic copolymer, EGDMA as a crosslinking agent, and 2H2M as a photoinitiator. Holmium (III) oxide, Europium (III) oxide, aluminum oxide, and PVP are used. When Holmium (III) oxide and Europium (III) oxide are added based on the Ref sample, the characteristics of the lens tend to be similar overall, and the aluminum oxide shows a tendency slightly different from the previous two oxides. This material can be used as a silicone lens material with various nano oxides and polyvinylpyrrolidone (PVP) acting as a dispersant.

A micromechanics-based time-domain viscoelastic constitutive model for particulate composites: Theory and experimental validation

  • You, Hangil;Lim, Hyoung Jun;Yun, Gun Jin
    • Advances in aircraft and spacecraft science
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    • v.9 no.3
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    • pp.217-242
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    • 2022
  • This paper proposes a novel time-domain homogenization model combining the viscoelastic constitutive law with Eshelby's inclusion theory-based micromechanics model to predict the mechanical behavior of the particle reinforced composite material. The proposed model is intuitive and straightforward capable of predicting composites' viscoelastic behavior in the time domain. The isotropization technique for non-uniform stress-strain fields and incremental Mori-Tanaka schemes for high volume fraction are adopted in this study. Effects of the imperfectly bonded interphase layer on the viscoelastic behavior on the dynamic mechanical behavior are also investigated. The proposed model is verified by the direct numerical simulation and DMA (dynamic mechanical analysis) experimental results. The proposed model is useful for multiscale analysis of viscoelastic composite materials, and it can also be extended to predict the nonlinear viscoelastic response of composite materials.

The Factors for the Formation of Carcinogenic N-Nitrosamine from Dried Marine Food Products (수산 건제품중 발암성 N-NITROSAMINE의 생성 요인)

  • SUNG Nak-Ju;KANG Shin-Kwon;LEE Soo-Jung;KIM Sung-Hee
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.27 no.3
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    • pp.247-258
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    • 1994
  • A total of 31 commercial dried marine food products, consisting of 14 fishes, 2 shellfishes and 2 seaweeds species were analyzed for their contents of precusors of N-nitrosamine such as dimethylamine(DMA), trimethylamine(TMA), trimethylamine oxide (TMAO), betaine and nitrate and nitrite nitrogen as factors of N-nitrosamine formation. Carcinogenic N-nitrosamines were extracted by a steam distillation apparatus and were analyzed for their components using a gas chromatography-thermal energy analyzer. N-nitrosodimethylamine(NDMA) was confirmed by a gas chromatography-mass spectrometry. The contents of betaine nitrogen in samples were in the range of $5.2{\sim}373.8mg\%$ and were significantly higher than tertiary amines such as TMA and TMAO. DMA nitrogen in those samples was in the range of trace-31.2ppm and was high, in the dried shark(31.2ppm), alaska pollack($22.9{\sim}24.3ppm$) and octopus($17.9{\sim}18.4ppm$). In dried laver and sea mustard, however, amines were not detected at all. The levels of nitrate nitrogen in the dried marine samples ranged from zero to 16.8ppm and were high in the dried stingray(16.8ppm), alaska pollack(16.3ppm) and squid($2.2{\sim}12.4ppm$), but were less than 1.0 ppm in other samples. The levels of nitrite nitrogen were lower than those of nitrate nitrogen and it was not detected in dried sea cucumber, laver and sea mustard. Twenty eight of 31 samples contained NDMA($range=1.2{\sim}86.0ppb$), which was the only volatile N-nitroso compound found. The NDMA levels of dried stingray($2.8{\sim}86.0ppb$), alaska pollack($8.2{\sim}55.5ppb$), squid($3.3{\sim}53.2ppb$), yellow corvenia($45.9ppb$) and plain dried shrimp($15.4{\sim}17.9ppb$) were high. However, it was not detected in dried sea cucumber, laver and sea mustard. Samples, containing high levels of NDMA, also contained high nitrate and nitrite nitrogen. From above results, it can be concluded that nitrate and nitrite were major factors for the formation of NDMA in dried marine food products.

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Changes of Oxidative Enzymes and Fatty Acid Composition of Bifidobacterium adolescentis and B. longum under Anaerobic and Aerated Conditions. (산소의 Stress에 따른 Bifidobacterium adolescentis와 Bifidobacterium longum의 산화효소의 활성과 세포 지방산 조성의 변화)

  • 신순영;박종현
    • Microbiology and Biotechnology Letters
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    • v.26 no.1
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    • pp.7-14
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    • 1998
  • To study the oxygen tolerance mechanism of bifidobacteria, we have studied the growth of cells, the activities of the enzymes which were related with oxygen, such as catalase, superoxide dismutase(SOD), NADH oxidase, and NADH peroxidase, and cellular fatty acid compositions of Bifidobacterium adolescentis and B. longum under anaerobic and aerated (microaerobic and aerobic) conditions. B. longum grew relatively well under the microaerobic conditions, whereas the growth of B. adolescentis was inhibited under the same aerated conditions. B. adolescentis had extremely low level of NADH oxidative enzymes while B. longum had the relatively high level of NADH oxidative enzymes, whose activities were dramatically increased from 3.7 to 11.4 times by microaerobic condition but not in B. adolescentis. The activity of SOD was unexpectedly high in B. adolescentis compared with in B. longum under anaerobic and aerated conditions. The activities of catalase were not detected in all samples tested in this study. We also found that normal $C_{l6:0}$ and $C_{18:1}$ were the major fatty acids in B. adolescentis and B. longum under anaerobic and aerated conditions. 2.2-14.1% $C_{l9:0}$ cyclo fatty acid was detected only in B. longum and the fatty acid was increased by the addition of the aeration. The $C_{l9:0}$ cyclic fatty acid was identified as a cis 9, 10-methylene octadecanoic acid, which was different from lactobacillic acid in the cyclized site. 6.6%-24.6% of dimethyl acetals (DMA) which came from plasmalogen were observed in the B. adolescentis and B. longum grown under anaerobic condition, and the components were notably decreased in the cells grown under the aerated conditions. It is believed that NADH oxidative enzymes play an important role to detoxify oxygen metabolites of Bifidobacteriurn spp. under anaerobic and microaerobic conditions. Independently from oxidative enzymes, it seems that oxygen stress may induce the change of the level of cellular fatty acids showing an increase of $C_{l9:0}$ cyclo in B. longum and a decrease of $C_{l8:1}$ of plasmalogen in B. longum and B. adolescentis to adapt in environment.

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Comparison of Total and Inorganic Arsenic Contamination in Grain and Processed Grain Foods (곡류 및 곡류 가공식품의 총비소 및 무기비소 오염 비교)

  • Eun-Jin, Baek;Myung-Gil, Kim;Hyun-Jue, Kim;Jin-Hee, Sung;You-Jin, Lee;Shin-Hye, Kwak;Eun-Bin, Lee;Hye-Jin, Kim;Won-Joo, Lee;Myung-Jin, Lee
    • Journal of Food Hygiene and Safety
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    • v.37 no.6
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    • pp.385-393
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    • 2022
  • The contamination level of inorganic arsenic, a human carcinogen, was investigated in 87 grains and 66 processed grain foods. Two inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) and four organic arsenic monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine were analyzed using HPLC-ICP/MS with high separation and sensitivity and ICP/MS was used to quantify total arsenic. Inorganic arsenic was detected in all grains. And the total arsenic in grains consists of about 70-85% inorganic arsenic and about 10-20% DMA. The concentration of inorganic arsenic was high in rice and black rice cultivated in paddy soil with irrigated water, while the miscellaneous grain in field was low. Mean concentration of inorganic arsenic in rice germ, brown rice and polished rice was 0.160 mg/kg, 0.135 mg/kg, 0.083 mg/kg, respectively, indicating that rice bran contains more arsenic. In processed grain foods, inorganic arsenic concentration varied according to the kind of ingredients and content, and the detection amount was high in processed food with brown rice and germ. The arsenic content of all samples did not exceed each standard, but the intake frequency is high and it is considered that continuous monitoring is necessary for food safety.