• Bulletin of the Korean Chemical Society
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• 제17권2호
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• pp.153-158
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• 1996

The synthesis of common skeleton of podosporin A and aureol was studied through cationic olefin cyclization as a key step. The generation of thermodynamic silyl enol ether or enol acetate under known conditions gave regioselectivity of 88:12. The enolate alkylation of 2,3-dimethylcyclohexanone with 2,5-dimethoxybenzyl bromide at the more substituted site via lithium enolate gave poor yield. In this case an organozincate or an ammonium enolate also proved to be ineffective or not practical in terms of yield. Side chain elongation of the substituted cyclohexanone 13 through Grignard reaction, Wittig reaction, or Shappiro reaction did not proceed because of steric hindrance and side reactions. However, Stille coupling reaction via enol triflate produced the desired product 18 in high yield. The advanced intermediate 22, which was efficiently synthesized from 18, produced 24 instead of the desired product under a cationic olefin cyclization condition, indicating that the cyclization occurred in a stepwise mannervia the organomercury intermediate 23.

• 대한화학회지
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• 제25권4호
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• pp.228-235
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• 1981

피리딘, ${\beta}$-피코린 및 3,5-루티딘과 요오드사이에 형성되는 전하이동착물을 사염화탄소 용액에서 자외선분광광도법을 사용하여 연구한 결과 $C_5H_5N{\cdot}I_2$, ${\beta}-C_5H_4(CH_3)N{\cdot}I_2$ 및 3,5-$C_5H_3(CH_3)_2N{\cdot}I_2$ 형의 1:1 분자착물이 형성됨을 알았다. 이들 착물생성에 대한 흡수최대는 온도가 상승함에 따라 blue shift되므로 이를 고려하여 각 온도에서의 평형상수를 구했다. 이 값으로부터 이들 착물생성에 대한 ${\Delta}H$, ${\Delta}G$및 ${\Delta}S$ 이 열역학적 파라미터를 산출하였다. 이 결과 착물의 상대적 안정도가 다음 순서로 증가함을 알수가 있었다. Pyridine < ${\beta}$-Picoline < 3,5-Lutidine. 이러한 결과는 dipole moment, steric hindrance effect 및 positive inductive effect에 의한 electron density의 증가 때문인 것으로 설명할 수 있었다. 그리고 polymethylbenzene-iodine CT-complex와도 비교 검토하였다.

• 공업화학
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• 제8권2호
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• pp.308-314
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• 1997

폴리우레탄 전선도료 제조시의 TDI와 MDI의 blocking 반응에 미치는 촉매와 blocking reagents(BR)의 영향에 대하여 조사하였다. 1,4-diazabicyclo[2.2.2]octane(DABCO)와 tetramethyl guanidine(TMG)와 같은 촉매들은 NCO의 blocking 반응을 완결시키는데 필요한 것으로 나타났다. TMG는 DABCO에 비해 매우 빠른 반응속도를 보였다. TMG의 농도는 1%까지 반응도에 대하여 정량적으로 비례하였다. DABCO의 경우는 0.25%의 농도에서 가장 높은 반응도를 나타내었다. BR의 입체영향을 알아보기 위해 phenol, p-cresol, m-cresol, o-cresol, 2,4-xylenol과 같은 BR 등을 사용하였다. 예측한대로 입체장애가 적은 BR이 높은 반응도를 보였다. 또한 이 반응 시스템에서는 온도와 BR의 농도가 증가할수록 반응도가 증가하였다.

• Journal of Microbiology and Biotechnology
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• 제6권3호
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• pp.173-178
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• 1996

Synergic effects among endo-xylanase, $\beta$-xylosidase, and acetyl xylan esterase of Bacillus stearothermophilus in the hydrolysis of xylan were studied by using birchwood, oat spelt, and acetylated xylan as substrates. Synergism between endo-xylanase and $\beta$-xylosidase was observed on all three substrates tested, indicating that $\beta$-xylosidase enhanced the production of xylose by relieving the end-product inhibition upon endo-xylanase conferred by xylooligomers. Endo-xylanase and $\beta$-xylosidase also showed synergism with acetyl xylan esterase in the hydrolysis of birchwood and acetylated xylan, while no synergic effect was detected in oat spelt xylan hydrolysis. Thus, the hydrolysis of xylan containing acetic acid side chains required the action of acetyl xylan esterase, which eliminated the steric hindrance of the side chains, leading to the better hydrolysis by endo-xylanase and $\beta$-xylosidase , and the acetyl xylan esterase activity was also enhanced by endo-xylanase and $\beta$-xylosidase for the latter enzymes provided acetyl xylan esterase with shorter xylan oligomers, the better substrate for the enzyme.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.212-212
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• 2012

The Coverage dependent attachment of multifunctional groups included in threonine molecules adsorbed to Ge (100)$-2{\times}1$ surface was investigated using core-level photoemission spectroscopy (CLPES) and density functional theory (DFT) calculations. The core-level spectra at a low coverage indicated that the both carboxyl and amine groups participated in the bonding with the Ge (100) surface by "O-H dissociated and N-dative bonded structure". However, at high coverage level, additional adsorption geometry of "O-H dissociation bonded structure" appeared possibly to minimize the steric hindrance between adsorbed molecules. Moreover, the C 1s, N 1s, and O 1s core level spectra confirmed that the carboxyl oxygen is more competitive against the hydroxymethyl oxygen in the adsorption reaction. The adsorption energies calculated using DFT methods suggested that four of six adsorption structures were plausible. These structures were the "O-H dissociated-N dative bonded structure", the "O-H dissociation bonded structure", the "Om-H dissociated-N dative bonded structure", and the "Om-H dissociation bonded structure" (where Om indicates the hydroxymethyl oxygen). These structures are equally likely, according to the adsorption energies alone. Conclusively, we investigate in threonine on Ge (100) surface system that the "O-H dissociated-N dative bonded structure" and the "O-H dissociation bonded structure" are preferred at low coverage and high coverage.

• 공업화학
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• 제31권1호
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• pp.67-72
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• 2020

Biomaterials are frequently functionalized with Arg-Gly-Asp (RGD) peptides to provide cell adhesion sites. In this study, RGD peptides were enzymatically coupled on to the surface of fibroin microspheres. Papain exhibited a strong preference for dansyl phenylalanine for the peptide formation with fibroin microspheres. Thus, RGD1 peptide was designed to carry cysteine to both sides of the sequence, glycine as a spacer and two residues of phenylalanine at the C-terminal (CRGDCGFF). The enzymatic modification facilitated by an increasing amount of substrate and by the presence of organic solvent, dimethylsulfoxide at 25% (v/v). Microspheres coupled with RGD1, showed a significantly different precipitation property and an increased apparent volume, possibly due to the steric hindrance of RGD peptides on the surface. Transmission electron microscopy also confirmed the presence of cysteine residues in RGD1 coupled on the surface of microspheres stained with gold nanoparticles. RGD1-microspheres significantly facilitated the growth of murine fibroblast 3T3 cells even under non-adhesion culture conditions.

• Elastomers and Composites
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• 제52권3호
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• pp.173-179
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• 2017

Side-chain liquid crystalline polymers having polysiloxane skeletons were synthesized by a thiol-ene reaction, using two kinds of mesogenic groups: a cholesteryl group for induction into a cholesteric liquid crystal phase and a triazomesogenic group for imparting light-sensitivity. All the synthesized polymers were crystalline, except the one with a single cholesteryl group. Crystallinity, glass transition temperature, and melt transition temperature increased with increasing content of the azomesogenic group. The polymer (P-C10A0) with a single cholesteryl group has a cholesteric phase, the one (P-C0A10) with a single azomesogenic group has a smectic phase, and those with both types of mesogenic groups showed both smectic and cholesteric phases. The temperature ranges of the two liquid crystalline phases in the co-polymers were independent of the contents of the two types of mesogenic groups. The rate of photoisomerization of the light-sensitive azobenzene group in the polymer decreased with increasing azobenzene content due to steric hindrance between the azomesogenic groups.

• 대한화학회지
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• 제50권5호
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• pp.369-373
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• 2006

Pd(CF3CO2)2-phosphine 및 Pd(CF3CO2)2-sulfide 계를 촉매로 사용하여 styrene의 아릴화반응을 연구하였다. 주 생성물인 trans-stilbene의 수율은 phosphine 치환체의 염기도가 증가할수록 높아졌고 입체장애가 클수록 낮아졌다. arylphosphine에서 styrene으로 aryl 기가 이동하는 현상은 동일한 arylphosphine에 대하여 Pd(CF3CO2)2의 경우가 더 높은 염기도를 가진 Pd(CH3CO2)2의 경우보다 더 많이 나타났으므로 이 반응은 Pd 이온이 먼저 aryl 기에 공격을 하는 친전자성 메커니즘에 의해 진행된다고 본다. 한편 Pd(CF3CO2)2-sulfide보다 Pd(CF3CO2)2-phosphine 계가 더 효과적인 촉매로 작용하였다.

• 대한화학회지
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• 제45권1호
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• pp.51-60
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• 2001

치환된 하이드록시 방향족 화합물과 이차아민, paraformaldehyde를 비 양성자성 용매하에서 one-pot으로 반응시켜 기질에 따른 상대적인 반응성을 비교하였으며, Mannich반응이 일어난 자리도 조사하였다. 치환된 하이드록시 방향족 고리의 Mannich반응의 반응성과 위치선댁성은 기질의 친핵성도와 아민의 입체장애에 의존함을 알 수 있었다.

• Macromolecular Research
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• 제11권6호
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• pp.471-475
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• 2003

A new poly[2-(2',5'-dimethylphenyl)-1,4-phenylenevinylene] (PDMPPV) that features a bulky 2',5'-dimethylphenyl substituent, which can induce steric hindrance between the PPV backbone and the methyl groups, was designed and synthesized. The polymer structure having no TBB defects was confirmed by $^1$H-NMR and $\^$13/CNMR spectroscopy. The polymer showed good thermal stability with high T$\_$g/. The polymer film showed a maximum absorption at 415 nm with an absorption onset at 480 nm. The maximum emission peak showed at ca. 515 nm, with a shoulder at 530 nm. The turn-on voltages of ITO/PEDOT/PDMPPV/Al and ITO/PDMPPV/Al devices were 8 and 10 V, respectively. The electroluminescence spectrum from the device showed a maximum peak at 510 nm with a shoulder at ca. 535 nm.