• Proceeding of EDISON Challenge
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• 2017.03a
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• pp.165-171
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• 2017

Diels-Alder 반응은 고리형 탄소화합물을 만드는 유기 합성 과정에서 매우 중요한 반응이다. 이 반응은 중간생성물 없이 오직 1 step으로 진행되는데, diene이나 dienophile에 결합한 치환기의 electron donating 및 electron withdrawing 성질에 따라 반응성이 달라진다고 알려져 있다. 이 때 반응물인 diene과 dienophile의 분자 오비탈 및 전이 상태의 에너지 변화를 계산화학을 통해 분석한다면 Diels-Alder 반응을 보다 심도 있게 이해할 수 있다. 이에 따라 본 연구에서는 DFT 계산을 통하여 치환기에 따른 활성화 에너지의 크기와 diene의 nucleophilicity 및 dienophile의 electrophilicity를 비교하였다. 이를 통해 electron withdrawing group의 경우 분자의 electrophilicity를 증가시키고, electron donating group의 경우 nucleophilicity를 증가시킨다는 것을 확인할 수 있었다. 그 결과, Diels-Alder 반응이 일어날 때 dienophile의 경우 치환된 electron withdrawing group에 의해 electrophilicity가 증가함에 따라 활성화 에너지가 낮아져 반응이 잘 일어나고, 반대로 diene의 경우 electron donating group이 치환되어 있을 때 nucleophilicity의 증가에 따라 반응이 잘 일어난다는 것을 알 수 있었다.

• Journal of the Korean Chemical Society
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• v.38 no.1
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• pp.21-25
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• 1994

The proton affinities of substituted imidazoles, relevant to the binding of lexitropsins that contain imidazole ring to the base pair (G-C sequence) of minor groove of DNA, are studied with the aid of EHT calculations. It is shown that proton affinity of imidazole substituted at position $\alpha$ to the basic nitrogen is slightly larger than that of imidazole substituted at N for the methylimidazole. Proton affinities of N-substituted imidazoles are found to be larger than those of imidazoles substituted at position ${\alpha}$ for a selected set of the other derivatives. As predicted the proton affinity increases when electron-donating group is attached at position N of imidazole.

• Journal of the Korea Concrete Institute
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• v.16 no.3 s.81
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• pp.319-326
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• 2004

This paper investigates the effect of the concrete containing mineral admixtures(pozzolanic materials such as fly-ash, ground granulated blast-furnace slag, silica fume and meta kaolin) on the resistance properties to chloride ion invasion. The purposed testing procedure was applied to the concrete replaced mineral admixtures for 3${\~}$4 replacement ratios under water-binder ratios ranged from 0.40 to 0.55. For the electro-migration test, Tang and Nilsson's method was used to estimate the diffusion coefficient of chloride ion. As a results, the water-binder ratios, kinds of mineral admixtures and replacement ratios, water curing periods had a great effect on the diffusion coefficient of chloride ion, and the optimal replacement ratios had a limitation for each mineral admixtures. Also, the use of mineral admixtures by mass(replacement of OPC) enhance the resistance ability against chloride penetration compared with the plain concrete. The compressive strength was shown related to the diffusion coefficient of chloride ion, the compressive strength increases with the diffusion coefficient of chloride ion decreasing. Below the 50 MPa, the variation of diffusion coefficient of concrete replaced mineral admixtures was bigger than that of plain concrete.

• Journal of the Korea Institute of Building Construction
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• v.16 no.1
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• pp.59-65
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• 2016

This study examined the compressive strength development and pH values of alpha-calcium sulfate hemihydrate(${\alpha}-CH$)-based binders developed for vegetation concrete with neutral pH between 6~7. Considering cost down and strength enhancement of the prepared binders, the ${\alpha}-CH$ was partially replaced by ground granulated blast furnace slag(GGBS), fly ash(FA), or ordinary Portland cement(OPC) by 25% and 50%. The compressive strength of mortars using 100% ${\alpha}-CH$ was 50% lower than that of 100% OPC mortars. With the increase of the replacement level of GGBS or FA, the compressive strength of ${\alpha}-CH$-based mortars tended to decrease, whereas the pH values were maintained to be 6.5~7.5. The main hydration products of ${\alpha}-CH$-based binders with GGBS or FA were a gypsum($CaSO_4$), whereas portlandite($Ca(OH)_2$) was not observed in such binders. Meanwhile, the pH values of ${\alpha}-CH$-based binders with OPC exceeded 11.5 due to the formation of $Ca(OH)_2$ phase as a hydration product. From the thermogravimetric analysis, the amount of $Ca(OH)_2$ in ${\alpha}-CH$-based binders with OPC was evaluated to be approximately 10% of the cement content.

• Journal of the Korea Concrete Institute
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• v.24 no.4
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• pp.435-444
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• 2012

High performance concrete mixes are selected and corresponding test specimens are made for the study of chloride diffusion coefficient at reference time. The concrete mixes were same designs as those used in construction of bridges located in a marine environment. Mix design variables included binder type, water-to-binder ratio, mineral admixtures to total binder weight substitution ratio, fine aggregate source, chemical water reducer admixture type for high strength and high flowability, and target slump or slump flow. The test results showed that the diffusion coefficients at reference time varied significantly according to the type of mineral admixtures and their substitution ratios. A model for diffusion coefficient at reference time considering the type of mineral admixture and the substitution ratio was developed. Diffusion coefficients from the developed model were compared with those from literature review, a previous model, and additional test results. All of the comparisons verified that the developed model can reasonably predict diffusion coefficients and the application of the model to the durability design against chloride penetration is appropriate.

• Applied Biological Chemistry
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• v.51 no.3
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• pp.171-176
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• 2008

The comparative molecular similarity indices analysis (CoMSIA) models between 3${\beta}$-Hydroxy-12-oleanen-28-oic acid (1-30) analogues as substrate molecule and their inhibitory activities ($pI_{50}$) against protein tyrosine phosphatase (PTP)-1B were derived and discussed quantitatively. Listing in order, the CoMFA>CoMSIA${\geq}$HQSAR>2D-QSAR model, these QSAR models had the better statistical values. The optimized CoMSIA F1 model at grid 3.0${\AA}$ had the best predictability and fitness ($q^2$=0.754 and $r^2$=0.976) by field fit alignment. The order of contribution ratio (%) of CoMSIA fields concerning the inhibitory activities was a H-bond acceptor (48.9%), steric field (25.8%) and hydrophobic field (25.4%), respectively. Therefore, the inhibitory activities of substrate molecules against PTP-1B were dependent upon H-bond acceptor field (A) of $R_4$-group. From the analytical results of CoMSIA contour maps, oleanolic acid derivatives will have better inhibition activities if $R_1$ group has H-bond acceptor disfavor, $R_3$group has steric disfavor and $R_4$ group has steric, hydrophobic, H-bond favor.

• Journal of the Society of Cosmetic Scientists of Korea
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• v.35 no.4
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• pp.271-276
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• 2009

The 3-dimensional quantitative structure-activity relationships (3D-QSARs) models between the substituents with changing groups ($R_1$ & $R_2$) of 4-($R_1$)-benzyl alcohol and 4-($R_2$)-phenol derivatives as substrate molecule and their inhibitory activities against tyrosinase were derived and discussed quantitatively. The optimized CoMSIA 2 model have best predictability and fitness ($r^2\;=\;0.858$ & $q^2\;=\;0.951$). The contour maps of optimized CoMSIA 2 model showed that, the inhibitory activities of the analogues against tyrosinase were expected to increase when hydrophobic favor, negative charge favor, steric disfavor and hydrogen bond donor disfavor groups were substituted at the $R^2$ position. When the positive charge and the hydrogen bond donor favor groups were substituted at the $R_1$ position, it is predicted that the substituents will be able to increase the inhibitory activity. However, hydrogen bond acceptor did not affect inhibitory activities of tyrosinase.

• Journal of the Korea institute for structural maintenance and inspection
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• v.12 no.5
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• pp.133-142
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• 2008

This paper studies the early-aged chloride binding capacity of various blended concretes including OPC(ordinary Portland cement), PFA(pulversied fly ash), GGBFS(ground granulated blast furnace slag) and SF(silica fume) cement paste. Cement pastes with 0.4 of a free water/binder ratio were cast with chloride admixed in mixing water, which ranged from 0.1 to 3.0% by weight of cement and different replacement ratios for the PFA, GGBFS and SF were used. The content of chloride in each paste was measured using water extraction method after 7 days curing. It was found that the chloride binding capacity strongly depends on binder type, replacement ratio and total chloride content. An increase in total chloride results in a decrease in the chloride binding, because of the restriction of the binding capacity of cement matrix. For the pastes containing maximum level of PFA(30%) and GGBFS(60%) replacement in this study, the chloride binding capacity was lower than those of OPC paste, and an increase in SF resulted in decreased chloride binding, which are ascribed to a latent hydration of pozzolanic materials and a fall in the pH of the pore solution, respectively. The chloride binding capacity at 7 days shows that the order of the resistance to chloride-induced corrosion is 30%PFA > 10%SF > 60%GGBFS > OPC, when chlorides are internally intruded in concrete. In addition, it is found that the binding behaviour of all binders are well described by both the Langmuir and Freundlich isotherms.

• Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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• 1999.04a
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• pp.33-33
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• 1999

고지 사용율을 증가시킴으로써 원가 절감을 모색하고 있는 국내 신문용지 생산업체에서 는 보류도와 탈수성 저하에 따른 생산성 악화가 발생하고 있을 뿐 아니라 제품의 강도 및 인쇄적성 저하라는 문제를 극복하는 것이 매우 중요한 과제로 대두되고 있다. 또 신문용지 생산공정의 수질이 악화됨에 따라서 사용되는 화학첨가제의 효능이 크게 감소하는 문제를 지니고 있다. 적합한 양성전분과 이러한 문제를 종합적으로 해결하기 위한 방안으로 신문용지 생산에 이의 적용기술을 모색하였다. 전기전도도가 4000 $\mu\textrm{s}$/cm인 신문용지 지료를 이용하여 DS 0.03인 저치환 양성 전분의 보류도 증가효과를 평가한 결과 양성전분을 사용하지 않은 경우에 비하여 보류도 증가율이 6 6%로 낮게 나타났으나, DS 0.06인 전분은 보류도 증가율이 21%로 향상효과가 높게 나타났 다. 또 양성전분의 치환도가 증가할수록 인장지수, 내부결합강도, 표면강도 향상 효과도 증 가되는 결과를 얻을 수 있었다. 가교 처리를 실시한 치환도 0.08 및 0.1의 습식양성전분의 경우에는 미세분 보류도, 여수도, 탁도 등에 큰 효과를 나타내지 않았다. 경우 보류도가 각 확인하였으며,이 건식방법으로 제조된 치환도 0.08 빛 0.15인 양성 전분을 0.5% 첨가할 각 16%, 21% 증가되어 적은 첨가량에서도 보류향상 효과가 높다는 것을 러한 효과는 여수도 및 양이온 요구량 측정을 통하여 재확인되었다. 저치환 양성전분의 성능을 개선시키기 위한 방법으로서 비이온성 천연고분자를 활용하 는 방안을 검토한 결과 비이온성 천연고분자를 병용함에 따라 보류도 증가율이 탁월하게 개 선되었으며, 인장지수, 내부결합강도, 표면강도 등에서도 같은 효과를 얻을 수 있었다.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.366-373
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• 1984

Methanolysis rates of benzylbenzenesulfonates, substituted both on the substrate (Y) and on the leaving group (Z), were determined in MeOH-MeCN mixtures. The results showed that the reaction proceeds via the dissociative $S_N2$ mechanism, in which bond breaking proceeds in greater degree compared to bond formation at the transition state(TS). Multiple Hammett correlation analysis showed that the cross term, ${\rho}_{YZ}$, is very small and hence the cross interaction of two substituents, Y and Z, at the TS is not important, supporting the dissociative $S_N2 $ type mechanism. While transition state variations predicted by the quantum mechanical model is shown to agree in general with the experimental results, those predicted by the potential energy surface model failed to account for the leaving group effect properly.