• 제목/요약/키워드: main chain length effect

검색결과 18건 처리시간 0.022초

[4-{4'-(니트로페닐아조)펜옥시카보닐}]알카노화 셀룰로오스들의 열방성 액정 거동 (Thermotropic Liquid Crystalline Behavior of [4-{4'-(Nitrophenylazo)phenoxycarbonyl}]alkanoated Celluloses)

  • 정승용;마영대
    • 폴리머
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    • 제33권1호
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    • pp.58-66
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    • 2009
  • 셀룰로오스 트리[4-{4'-(니트로페닐아조)펜옥시카보닐}]알카노에이트들(NACEn, n=2$\sim$8,10, 유연격자 중의 메틸렌 단위들의 수)의 동족체들의 열방성 액정 특성을 검토하였다. 모든 동족체들은 단방성 네마틱 상들을 형성하였다. 액체 상에서 네마틱 상으로의 전이온도($T_{iN}$)는 n이 증가함에 따라 낮아지나 n이 7이상에서 거의 일정하게 되었다. $T_{iN}$에서의 엔트로피 변화와 n의 관계를 나타낸 그림 상에는 n=7에서 급격한 엔트로피의 감소가 관찰되었다. n=7에서 급격한 변화는 곁사슬 그룹의 배열의 차이에 의해 초래되는 것으로 생각된다. 용융온도($T_m$)와 $T_m$에서의 엔트로피 변화는 $T_{iN}$$T_{iN}$에서의 엔트로피 변화와 판이하게 뚜렷한 홀수-짝수 효과를 나타냈다. 이러한 사실은 네마틱 상과 결정 상에서의 곁사슬 그룹들의 평균적인 형태가 판이함을 시사한다. NACEn에서 관찰되는 네미틱상의 열적 안정성과 질서도는 아조벤젠 혹은 바이페닐 단위들을 곁사슬로 지닌 곁사슬형 그리고 복합형 액정 고분자 동족체들에 대해 보고된 결과들과 현저히 달랐다. 이들의 결과를 주사슬의 화학구조와 유연성, 주사슬과 곁사슬 그룹의 결합양식 그리고 반복단위당의 mesogenic 단위들의 수의 차이들의 견지에서 검토하였다.

Schiff Base 단일- 및 이메소제닉화합물의 액정성 (Liquid Crystalline Properties of Schiff Base Mono- and Dimesogenic Compounds)

  • 박주훈;최옥병;이진석;강근명;신주철;김기환;김학진;이창준;소봉근;이수민
    • Korean Chemical Engineering Research
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    • 제43권1호
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    • pp.176-180
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    • 2005
  • 방향족 Schiff base 메소제닉 단위와 폴리메틸렌 유연격자로 이루어진 한 계열의 주사슬 액정중합체와 네 계열 화합물의 액정성을 살펴보았다. 이들의 열적 성질과 액정성은 시차 주사 열분석기와 가열판이 부착된 편광현미경에 의하여 조사하였다. 중합체와 화합물 액정상의 성질은 중앙 폴리메틸렌 유연격자와 말단 알콕시기의 길이에 크게 의존하였다. 중합체 I과 계열 III 화합물은 녹는점과 등방성액체화 전이온도에서 짝수-홀수 효과를 보여 주었으나 계열 II와 IV 화합물은 등방성액체화 전이온도에서만 짝수-홀수 효과를 나타내었다. 편광현미경을 통하여 이들의 광학구조를 관찰하였을 때 네마틱과 스멕틱 액정상을 형성하였다.

폴리[1-{4-{4'-시아노페닐아조)펜옥시알킬옥시}에틸렌]들의 열방성 액정 거동 (Thermotropic Liquid Crystalline Behavior of Poly[1-{4-(4'-cyanophenylazo)phenoxyalkyloxy}ethylene]s)

  • 정승용;이재윤;마영대
    • 폴리머
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    • 제33권4호
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    • pp.297-306
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    • 2009
  • 폴리(비닐 알코올)과 1-{4-(4'-시아노페닐아조)펜옥시}알킬브롬들(CAFBn, n=$2{\sim}10$)을 이용하여 곁사슬형 액정 동족체들인 폴리 [1-(4-(4'-시아노페닐아조)펜옥시알킬옥시)에틸렌]들(CAFETn, n=$2{\sim}10$, 유연격자중의 메틸렌 단위들의 수)을 합성함과 동시에 이들의 열방성 액정 특성을 검토하였다. n=$2{\sim}5$인 CAPBn은 액정 상들을 형성하지 않는 반면 CAPB6 그리고 n=$7{\sim}10$인 CAPBn들은 각각 쌍방성 그리고 단방성 네마틱 상들을 형성 하였다. 이러한 사실과 판이하게, CAPETn 고분자들 중에서 CAPET5만이 쌍방성 네마틱 상을 형성하는 반면 나머지 고분자들은 단방성 네미틱 상들을 형성하였다. CAPETn들의 액체 상에서 네마틱 상으로의 전이온도들 그리고 CAPBn들에 비해 큰 값들을 갖는 CAPETn들의 상 전이시의 엔트로피 변화는 n의 함수로서 전형적인 홀수-짝수 효과를 나타냈다. 이러한 상 전이 거동들을 Imrie에 의한 'virtual trimer model'의 견지에서 검토하였다. CAPETn들의 액정 상의 특성들은 폴리아크릴레이트, 폴리메타크릴레이트 그리고 폴리스티렌에 (시아노페닐아조)펜옥시 그룹들을 플리메틸렌 유연격자들을 통하여 연결시켜 얻은 고분자들에 대해 보고된 결과와 크게 달랐다. 이러한 결과들은 주사슬과 곁사슬 그룹의 화학적 결합양식이 액정 상의 형성능, 안정성 그리고 구조에 중요한 역할을 함을 시사한다.

폴리[1-{4-(4'-니트로페닐아조)페녹시카보닐알카노일옥시}에틸렌]들의 열방성 액정 거동 (Thermotropic Liquid Crystalline Behavior of Poly[1-{4-(4'-nitrophenylazo)phenoxycarbonylalkanoyloxy}ethylene]s)

  • 정승용;마영대
    • 폴리머
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    • 제32권5호
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    • pp.489-496
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    • 2008
  • 폴리 [1-{4-(4'-니트로페닐아조)페녹시카보널알카노일옥시}에틸렌]들(NAPEn, n=$2{\sim}8$,10, 유연격자 중의 메틸렌 단위들의 수)의 동족체들의 열방성 액정 거동을 검토하였다. 모든 동족체들은 단방성 네마틱 상들을 형성하였다. 유리전이온도들은 n이 증가함에 따라 낮아졌다. 이러한 사실은 곁사슬 그룹들에 의한 주사슬의 가소화에 의해 초래되는 것으로 생각된다. 액체 상에서 네마틱 상으로의 전이온도들은 n이 7까지는 낮아지며 홀수-짝수 효과를 나타냈다. 그러나 n>7인 동족체들의 전이온도는 거의 일정하게 되었다. 이러한 거동은 유연격자의 홀수-짝수의 변화에 기인한 곁사슬의 평균적인 형태변화의 견지에서 합리적으로 설명된다. 전이온도에서 관찰되는 엔트로피 증가의 변화도 동일한 관점에서 설명된다. NAPEn이 나타내는 액정 특성들은 폴리아크릴레이트, 폴리메타크릴레이트 그리고 폴리스틸렌에 아조벤젠 그룹들을 폴리메틸렌 유연격자들을 통하여 연결시켜 얻은 고분자들에 대해 보고된 결과와 전혀 달랐다. 이러한 결과들은 주사슬과 곁사슬의 화학적 결합양식이 액정상의 형성능, 안정성 그리고 구조에 중요한 역할을 함을 시사한다.

Cyclin D1 Gene G870A Variants and Primary Brain Tumors

  • Zeybek, Umit;Yaylim, Ilhan;Ozkan, Nazli Ezgi;Korkmaz, Gurbet;Turan, Saime;Kafadar, Didem;Cacina, Canan;Kafadar, Ali Metin
    • Asian Pacific Journal of Cancer Prevention
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    • 제14권7호
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    • pp.4101-4106
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    • 2013
  • Alterations of cyclin D1, one of the main regulators of the cell cycle, are known to be involved in various cancers. The CCDN1 G870A polymorphism causes production of a truncated variant with a shorter half-life and thus thought to impact the regulatory effect of CCDN1. The aim of the present study was to contribute to existing results to help to determine the prognostic value of this specific gene variant and evaluate the role of CCDN1 G870A polymorphism in brain cancer susceptibility. A Turkish study group including 99 patients with primary brain tumors and 155 healthy controls were examined. Genotypes were determined by polymerase chain reaction-restriction fragment length polymorphism analysis. The CCDN1 genotype frequencies in meningioma, glioma and control cases were not significantly different (p>0.05). No significant association was detected according to clinical parameters or tumor characteristics; however, a higher frequency of AG genotype was recorded within patients with astrocytic or oligoastrocytic tumors. A significant association between AG genotype and gliobilastoma multiforme (GBM) was recorded within the patients with glial tumors (p value=0.048 OR: 1.87 CI% 1.010-3.463). According to tumor characteristics, no statistically significant difference was detected within astrocytic, oligoasltrocytic tumors and oligodentrioglias. However, patients with astrocytic astrocytic or oligoastrocytic tumors showed a higher frequency of AG genotype (50%) when compared to those with oligodendrioglial tumors (27.3%). Our results indicate a possible relation between GBM formation and CCDN1 genotype.

Properties of the Microinterface formed by Phosphatidylcholine and 1-Butanol as Reaction Media of Hydrolysis of Phosphatidylcholine

  • Yamazaki, Keiju;Imai, Masanao;Suzuki, Isao
    • 한국막학회:학술대회논문집
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    • 한국막학회 2004년도 Proceedings of the second conference of aseanian membrane society
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    • pp.82-85
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    • 2004
  • Microinterface of W/Omicroemulsion prepared by phosphatidylcholine was used as reaction media of hydrolysis of phosphatidylcholine by phospholipaseA$_2$. Phosphatidylcholine was used as an amphiphile and was acted as a substrate. Organic phase of W/Omicroemulsion in this study was prepared by mixed organic solvents i.e. 2,2,4-trimethylpentane (isooctane) as a main solvent and 1-butanol as a co-solvent. The effect of added 1-butanol was remarkable not only on reaction beginning but also on high reaction rate. The hydrolysis reaction was dramatically initiated when 1-butanol was injected into the running isooctane/PC system. The enhancement by 1-butanol addition into single organic solvent was our original finding compare with previous conventional organic solvent. The reaction rate was elevated by the added amount of 1-butanol. The enhanced reaction rate was about 150-folds. This enhancement was speculated as 1-butanol adsorption on the microinterface. The adsorbed 1-butanol improved the properties of microinterface, especially its mobility was increased by difference of the chain length between phosphatidylcholine and 1-butanol. PhospholipaseA$_2$ molecules were located on the microinterface due to modified mobility of microinterface. Located phospholipaseA$_2$ on the microinterface reacted easily with phosphatidylcholine molecule. As a result high reaction rate was obtained. Microinterfacial properties were successfully improved by adsorbed 1-butanol molecule, and were favorable to appear higher reactivity of phospholipaseA$_2$.

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환경친화적 LE-형 비이온계면활성제를 사용한 반연속식 말브틸-아크릴레이트/메틸메타-아크릴레이트 유화중합에 관한 연구 (Semi-continuous Emulsion Polymerization of n-Butyl acrylate/Methyl metacrylate using Environmental-Friendly LE-Type Nonionic Surfactant)

  • 김철웅
    • 청정기술
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    • 제11권1호
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    • pp.41-50
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    • 2005
  • 본 연구는 환경친화적인 선형 비이온 계면활성제인 LE-형유화제를 사용하여 점착성분의 단량체로 노말부틸 아크릴레이트 (n-butyl acrylate, n-BA)와 응집성분의 단량체로 메틸메타 아크릴레이트 (methyl metacrylate, MMA)를 사용하여, 폴리머 시멘트용 아크릴계 에멀젼 수지를 제조하기 한 최적조건을 얻기 위해 수용액상에서 유화중합을 실시하였다. 실험결과, 사용한 계면활성제 (LE-형)의 친수성인 체인 길이(n)의 값이 증가할수록 응석의 발생이 줄어들어 안정한 폴리머 에멀젼을 얻을 수 있었다. 최종 폴리머 에멀젼의 농도는 이 계면활성제의 사용량을 증가시킴에 따라 증가하다가 어느 농도 이상에서 응석의 발생이 거의 없는 폴리머 에멀젼을 얻을 수 있었으며, 반면에 평균 입자크기도 사용량에 따라 작아지다가 250 nm로 일정한 크기를 나타내었다. 또한 기능성 폴리머로서 보조모노머의 첨가는 최종 폴리머 에멀젼의 응석과 입자크기에 크게 영향을 미쳤는데, 주 모노머에 보조 모노머인 아크릴산 (acrylic acid, AA)과 아크릴 아마이드 (acrylic amide, AM)의 혼합하여 첨가한 경우, 첨가하지 않은 경우에 비해 응석의 발생이 줄어들어 안정한 폴리머 에멀젼을 얻을 수 있었다. 최적조건에서 어진 아크릴 폴리머 에멀젼은 평균 입자크기 200-300 nm, 제타전위 (zeta potential)값 -50 mv 정도였으며, 단일 유리전이온도 (glass temperature, Tg)를 가진 고분자 나노 입자가 수용액상에 잘 분산되어 있음을 알 수 있었다. 따라서 중합조건을 최적화시켜 안정된 폴리머 에멀젼을 얻을 있었다.

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Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 한국균학회 2016년도 춘계학술대회 및 임시총회
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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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