• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.993-999
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• 1998

Acid catalyzed hydrolysis of 1-phenoxyethyl propionate, Ⅰ, has been studied using the PM3 method in the gas phase. The first step of the reaction is the protonation of basic sites, three different oxygens in Ⅰ, producing three protonated species Ⅱ, Ⅲ and Ⅳ. All possible reaction pathways have been studied from each protonated structure. Changes in the reaction mechanisms have also been discussed from the results obtained by varying a nucleophile from a water monomer to a water dimer to a complex between one water molecule and an intermediate product (propionic acid or phenol) produced in the preceding unimolecular dissociation processes. Minimum energy reaction pathway is 2-W among the possible pathways, in which water dimer acts as an active catalyst and therefore facilitates the formation of a six-membered cyclic transition state. Lower barrier of 2-W is ascribed to an efficient bifunctional catalytic effect of water molecules. PM3-SM3.1 single point calculations have been done at the gas-phase optimized structure (SM3.1/PM3//PM3) to compare theoretical results to those of experimental work.

• Bulletin of the Korean Chemical Society
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• 제22권9호
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• pp.999-1004
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• 2001

(1-Chloro-2,2-dicyanovinyl)benzene or 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene was reacted with 2-amino-phenol to give the model compound, hydroxy enaminonitrile, which was found to undergo thermal cyclization reaction to form the corresponding benzoxazole. This intramolecular cyclization reaction is expected to occur through nucleophilic attack to electropositive enamine carbon by ortho-hydroxy group on the phenyl ring, which is accompanied by the release of neutral malononitrile through rearrangement. From each bifunctional monomer, o-hydroxy substituted polyenaminonitrile was prepared and characterized as a new precursor polymer for well-known aromatic polybenzoxazole. Also the unusual macrocyclic dimer formation from the 1,4-bis(1-chloro-2,2-dicyanovinyl)benzene and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane polymerization reaction system was discussed. The thermal cyclization reactions and the properties of polymers were investigated using FT-IR and thermal analysis (DSC & TGA).

• Bulletin of the Korean Chemical Society
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• 제19권2호
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• pp.155-159
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• 1998

o-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl o-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (5b), p-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of o-(2-vinyloxyethoxy)benzaldehyde (1), m-(2-vinyloxyethoxy)benzaldehyde (2), and p-(2-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 4a-b and 6a-b polymerized readily with cationic initiators to give polymers with the NLO-chromophores o- and p-oxybenzylidenemalononitrile or o- and p-oxybenzylidenecyanoacetate in side chain at -60 ℃, while meta-isomers 5a and 5b gave lower yields of polymers under the same conditions. The resulting polymers 7-9 were soluble in common organic solvents and the inherent viscosities of polymers were in the range of 0.20-0.30 dL/g in acetone. Solution-cast films were clear and brittle, showing Tg values in the range of 40-70 ℃.

• Journal of Electrochemical Science and Technology
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• 제13권1호
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• pp.120-127
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• 2022

Molybdenum disulfide (MoS₂) has been widely used as a catalyst for the bifunctional activities of hydrogen and oxygen evolution reactions (HER and OER). Here, we investigated size dependent HER and OER performance of MoS₂. The smallest size (90 nm) of MoS₂ exhibits the lowest overpotential of -0.28 V at -10 mAcm^-2 and 1.52 V at 300 mAcm^-2 with the smallest Tafel slopes of 151 and 176 mVdec^-1 for HER and OER, respectively, compared to bigger sizes (2 ㎛ and 6 ㎛) of MoS₂. The better HER and OER performance is attributed to high electrochemical active surface area (6 × 10^-4 cm²) with edge sites and low charge transfer resistance (18.1 Ω), confirming that the smaller MoS₂ nanosheets have the better catalytic behavior.

• 한국미생물·생명공학회지
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• 제39권1호
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• pp.9-19
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• 2011

Bacillus subtilis의 pyrimidine biosynthetic (pyr) operon은 UMP의 de nove 생합성에 관여하는 enzyme들을 encode할 뿐만 아니라, 조절단백질인 PyrR도 encode한다. PyrR은 pyr mRNA-binding 조절 기능과 uracil phosphoribosyltransferase activity를 동시에 가지는 bifunctional 단백질이다. 본 연구에서는 Proteomic analysis를 이용하여 Uracil - 환경에서 DB104${\Delta}$pyrR의 단백질 패턴을 분석하여 단백질 레벨에서 PyrR 단백질의 실질적인 조절 양상을 관찰하였다. 두 균주의 세포질 단백질은 다양한 발현의 차이를 보였으며, Silver 염색된 2D-gel의 pI 4~10 사이에서는 1,300여개의 단백질이 검출되었으며, 단백질 발현 차이를 보이는 172개의 spot 중에서 42개의 단백질이 identification 되었다. 그 결과 pyr operon의 단백질(PyrAa, PyrAb, PyrB, PyrC, PyrD, and PyrF)이 모두 Up regulation이 이루어지고 있음을 확인할 수 있었으며, 이것은 단백질 레벨에서 Pyrimidine 생합성 과정이 PyrR에 의해서 정확히 Regulation 되어짐을 확인할 수 있었다. 또한 Pyrimidine 생합성의 Up regulation과 Down regulation 상태의 단백질의 패턴 양상도 분석할 수 있게 되었다. Pyrimidine의 생합성 과정은 DNA를 구성하는 기본적인 구성 요소를 생산하는 과정으로서 여러가지 Metabolism 가운데 중요한 위치를 차지하고 있다. 만약 Pyrimidine의 생합성 과정이 Over- expression된다면 다른 Metabolism의 균형에도 변화가 올 것이다. Proteomics Analysis에 이용한 DB104${\Delta}$pyrR 균주는 Pyrimidine 생합성의 조절에 관여하는 PyrR knock out 균주로서 Uracil - 환경에서는 전체적인 Pyrimidine 생합성 조절이 Up regulation이 되어지므로 Up regulation 동안 어떤 Metabolism에 영향을 주는지 관찰을 할 수 있게 되었다. 특히 Amino Acid Metabolism에 관계있는 단백질의 Up regulation이 이루어짐을 관찰할 수 있었으며 이것은 현재 각광을 받고 있는 단백질 산업에 응용함으로써 산업적으로 많은 기대를 할 수 있을 것으로 예상되어진다.

• 폴리머
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• 제38권4호
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• pp.411-416
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• 2014

극성을 띠고있어 응집되는 성향이 카본블랙에 비해 강한 실리카의 분산도는 고무 복합소재의 물성을 좌우하는 중요한 요소이다. Wolff는 입자간 상호계수(${\alpha}_F$)를 도입하여 충전제간의 구조발달을 최초로 표현하였다. 하지만, 양기능성 실란의 도입에 따라 형성되는 3차원 구조발달은 표현할 수 없었다. 후에 이를 보완하기 위하여 Wolff의 표현은 복합소재 내 ${\alpha}_F$를 포함하는 구조발달 상호계수 ${\alpha}_C$로 확장되어 표현되었지만, 실험적으로 이 표현을 증명한 연구는 없었다. 이 논문은 구조발달 상호계수인 ${\alpha}_C$를 ${\alpha}_F$(실리카-실리카간 구조발달 상호계수), ${\alpha}_{FP}$(실리카-실란-고무간 구조발달 상호계수), ${\alpha}_P$(고무-고무간 구조발달 상호계수)로 고려하여 단기능성 및 양기능성 실란으로 처리된 실리카가 함유된 복합소재를 실험에 의해 최초로 표현하였다. 구조가 다른 실란들(PTES, OTES, TESPD, TESPT)을 이용하여 구조발달 상호계수 ${\alpha}_C$를 구성하는 ${\alpha}_F$, ${\alpha}_{FP}$, ${\alpha}_P$의 수치들을 측정하고 계산하였다. TESPT가 첨가된 복합소재의 ${\alpha}_C$의 값은 1.64이며, 이를 구성하고 있는 ${\alpha}_F$, ${\alpha}_{FP}$, ${\alpha}_P$는 각각 0.99, 0.31, 0.34로 나타났다.

• The Korean Journal of Physiology and Pharmacology
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• 제21권6호
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• pp.591-598
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• 2017

Propofol is known to cause vasorelaxation of several systemic vascular beds. However, its effect on the pulmonary vasculature remains controversial. In the present study, we investigated the effects of propofol on human pulmonary arteries obtained from patients who had undergone surgery. Arterial rings were mounted in a Multi-Myograph system for measurement of isometric forces. U46619 was used to induce sustained contraction of the intrapulmonary arteries, and propofol was then applied (in increments from $10-300{\mu}m$). Arteries denuded of endothelium, preincubated or not with indomethacin, were used to investigate the effects of propofol on isolated arteries. Propofol exhibited a bifunctional effect on isolated human pulmonary arteries contracted by U46619, evoking constriction at low concentrations ($10-100{\mu}m$) followed by secondary relaxation (at $100-300{\mu}m$). The extent of constriction induced by propofol was higher in an endothelium-denuded group than in an endothelium-intact group. Preincubation with indomethacin abolished constriction and potentiated relaxation. The maximal relaxation was greater in the endothelium-intact than the endothelium-denuded group. Propofol also suppressed $CaCl_2$-induced constriction in the 60 mM $K^+$-containing $Ca^{2+}$-free solution in a dose-dependent manner. Fluorescent imaging of $Ca^{2+}$ using fluo-4 showed that a 10 min incubation with propofol ($10-300{\mu}m$) inhibited the $Ca^{2+}$ influx into human pulmonary arterial smooth muscle cells induced by a 60 mM $K^+$-containing $Ca^{2+}$-free solution. In conclusion, propofol-induced arterial constriction appears to involve prostaglandin production by cyclooxygenase in pulmonary artery smooth muscle cells and the relaxation depends in part on endothelial function, principally on the inhibition of calcium influx through L-type voltage-operated calcium channels.

• Applied Biological Chemistry
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• 제35권3호
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• pp.191-195
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• 1992

강낭콩 잎에서 에틸랜에 의하여 유도되는 분자량 30KD인 염기성 키틴분해효소를 정제하고 그 항균활성을 연구하였다. 이 단백질은 chitinase 활성과 lysozyme 활성을 가졌으며, Aspergillus fumigatus, Botrytis cinerea, Fusarium oxysporum, Rhizoctonia solani의 균사 생장을 억제하였다. 그러나 함께 실험한 2종류의 미생물 chitinase, 달걀 lysozyme, 파파야 protease는 이들에 대한 항균작용을 갖지 않았다. 이상의 결과는 lysozyme 활성을 가진 식물 chitinase가 병원균의 균사생장을 억제하여 자신을 방어할 수 있음을 시사한다.

• Macromolecular Research
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• 제15권1호
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• pp.74-81
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• 2007

A series of photoreactive mesogens based on chalcone were prepared and their morphological behavior and reactivity were studied according to a variable number of alkyloxy tail carbons. The linear ester compounds 3a-h comprised two chalcone units connected to a benzene ring through ester linkages. All linear ester compounds showed enantiotropic liquid crystalline phases. The X-ray diffractograms for the mesophases of compounds 3a-h showed a set of reflections in the small-angle region which consisted of more than three sharp diffraction peaks with d spacings in the ratio of 1:1/2:1/3, confirming the well defined smectic A structures of the compounds. Compounds 3a-h were considered to be bifunctional monomers due to the presence of two photoreactive chalcone groups. Upon UV irradiation, its polymerization proceeded through the [2+2] addition reaction between chalcone units in a stepwise manner. An image pattern was obtained by the photopolymerization of the liquid crystal of the compound (3h) with decyloxy tails through a photomask. The irradiated part became dark while the masked part remained birefringent under polarized optical microscopy, which was ascribed to the production via the UV irradiation of a polymer or a dimer having cyclobutane rings by [2+2] addition, which thereby disrupted the alignment of the molecules.

• 대한핵의학회지
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• 제39권4호
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• pp.215-223
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• 2005

Current interest in the regioselective N-functionalization of tetraazacycloalkanes (cyclen and cyclam) stems mainly from their complexes with radioactive metals for applications in diagnostic ($^{64}Cu,\;^{111}In,\;^{67}Ga$) and therapeutic ($^{90}Y$) medicine, and with paramagnetic ions for magnetic resonance imaging ($Gd^{+3}$). Selective methods for the N-substitution of cyclen and cyclam is a crucial step in most syntheses of cyclen and cyclam-based radiometal complexes and bifunctional chelating agents. In addition, mixing different pendent groups to give hetero-substituted cyclen derivatives would be advantageous in many applications for fine-tuning the compound's physical properties. So far, numerous approaches for the regioselective N-substitution of tetraazacycloalkanes and more specifically cyclen and cyclam are reported. Unfortunately, none of them are general and every strategy has its own strong points and drawbacks. Herein, we categorize numerous regioselective N-alkylation methods into three strategies, such as 1) direct substitution of the macrocycle, 2) introductiou of the functional groups prior to cyclization, and 3) protection/iunclionallrationideproteclion. Our discussion is also split into the methods of mono- and tri-functionalization and di-functionalizataion based on number of substituents. At the end, we describe new trials for the new macrocycles which iorm more stable metal complexes with various radiometals, and briefly mention the commercially available tetraazacycloalkanes which are used for the biconjugation of biomolecules.