• Mass Spectrometry Letters
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• 제13권3호
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• pp.49-57
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• 2022

During electrospray ionization mass spectrometry (ESI-MS) analysis of proteins, the addition of supercharging agents allows for adjusting the maximal charge state, affecting the charge state distribution, and increases the number of ions reaching the detector thus, improving signal detection. We postulate that in di-substituted arene isomers, molecules with higher polarizability values should generate greater interactions and hence elicit higher signal intensities. Polarizability is an electronic parameter which has been demonstrated to predict many chemical interactions. Many properties can be predicted based on charge polarization. Molecular polarizability is a vital descriptor for explaining intermolecular interactions. We employed DFT (density functional/Hartree-Fock hybrid model, B3LYP)-derived descriptors and computed molecular polarizability for ten disubstituted arene reagents, each set made up of three (ortho, meta, para) isomers, with reported use as supercharging reagents during ESI experiments. The atomic electronic inputs were ionization potential (IP), electron affinity (EA), electronegativity (𝛘), hardness (η), chemical potential (µ), and dipole moment (D). We determined that the para isomers showed the highest polarizability values in nine of the ten sets. There was no difference between the ortho and meta isomers. Polarizability also increased with increasing complexity of the substituents on the benzene ring. Polarizability correlated positively with IP, EA, 𝛘, η, and D but correlated negatively with chemical potential. This DFT study predicts that the para isomers of di-substituted arene isomers should elicit the strongest ESI responses. An experimental comparison of the three isomers, especially of larger supercharging molecules, could be carried out to establish this premise.

• 한국광학회지
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• 제27권6호
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• pp.223-228
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• 2016

액정과 같은 단축 이방성 분자들의 정렬 정도에 따라 달라지는 복굴절으로부터 상대 복굴절 ${\Delta}n_{rel}$를 구하고 ${\Delta}n_{rel}$과 방향질서변수(orientational order parameter) S의 관계를 탐색하였다. 무질서한 분포를 하고 있는 경우를 포함하여 액정의 정렬정도를 달리 표현할 수 있는 분포함수를 도입하고 이 분포함수를 사용하여 질서변수 S가 0부터 1까지 변하도록 액정분자들의 정렬정도를 달리하며 ${\Delta}n_{rel}$과 S를 수치계산 하였다. 이 계산 결과로부터 s와 ${\Delta}n_{rel}$는 $S=(1+a){\Delta}n_{rel}-a{\Delta}n^2_{rel}$와 같이 준선형적인 관계를 만족하며 a는 $n_o{\frac{{\Delta}n}{4}}$으로 근사할 수 있음을 확인하였다. 또한 복굴절으로부터 Vuks의 방법에 따라 구한 분자분극의 이방성과 Neugebauer의 방법에 따라 구한 분자분극의 이방성이 각각 질서변수 S와 또 다른 준선형 관계식들을 따름을 보였다.

• EDISON SW 활용 경진대회 논문집
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• 제4회(2015년)
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• pp.117-123
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• 2015

본 연구에서는 DFT를 이용하여 Nucleophilicity와 Basicity의 연관성에 대한 계산화학적 분석을 수행하였다. Basicity는 선정된 모델 분자의 protonation 반응에서 생성물과 반응물의 enthalpy 변화량인 양성자 친화도(Proton affinity, PA) 값을 구하여 분석하였다. 계산한 결과는 실험을 통해 얻은 PA 결과와 경향성이 거의 일치함을 확인하였다. Nucleophilicity는 모델 분자들과 $CH_3Br$ (electrophile)의 $SN_2$반응에서 gibbs free energy of activation(${\Delta}G^{\ddag}$) 값으로 그 경향성을 분석하였다. 또한 용매의 종류를 다르게 하여 용매에 따른 ${\Delta}G^{\ddag}$ 값의 경향성도 확인하였다. 각 용매에 따라 구한 ${\Delta}G^{\ddag}$와 PA의 상관관계를 비교하였으나, 큰 연관성은 보이지 않았다. 이에 ${\Delta}G^{\ddag}$와 PA의 상관관계를 보여줄 수 있는 parameter를 찾기 위하여 각 모델 분자의 Electronegativity와 Polarizability를 계산하여 연관성을 비교해보았다. Polarizability를 적용했을 때 Nucleophilicity와 Basicity사이의 연관성을 나타낼 수 없었던 반면, Electronegativity를 적용하여 Basicity와 Nucleophilicity의 연관성 보일 수 있음을 이론적으로 규명하였다.

• Archives of Pharmacal Research
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• 제20권1호
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• pp.1-6
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• 1997

We determined the microviscosity of synaptosomal plasma membrane vesicles (SPMV) isolated from bovine cerebral cortex and liposomes of total lipids (SPMTL) and phospholipids (SPMPL) extracted from SPMV. Changes in the microviscosity induced by the range and rate of lateral diffusion were measured by the intramolecular excimerization of 1, 3-di(1-pyrenyl)propane (Py-3-Py). The microviscosity values of the direct probe environment in SPMV, SPMTL and SPMPL were 38.17, 31.11 and 27.64 cP, respectively, at$37^{\circ}C$and the activation energies $(E_a)$ of the excimer formation of Py-3-Py in SPMV, SPMTL and SPMPL were 8.236, 7.448 amd 7.025 kcal/mol, respectively. Probe location was measured by polarity and polarizability parameters of the probe Py-3-Py and probe analogues, pyrene, 1-pyrenenonanol and 1-pyrenemethyl-3${\beta}$-hydroxy-22, 23-bisnor-5-cholenate (PMC), incorporated into membranes or solubilized in reference solvents. There existed a good linear relationship between the first absorption peak of the $^1_a$ band and the polarizability parameter $(n^{2}-1)/(2n^{2}+1)$.The calculated refractive index values for SPMV, SPMTL and SPMPL were close to 1.50, which is higher than that of liquid paraffin (n=l.475). The probe location was also determined by using a polarity parameter $(f-1/2f^{I})$. Here f=$({\varepsilon}-1)/(2{\varepsilon}+1)$ is the dielectric constant function and $f^I=(n^2-1)/(2n^2+1)$ is the refractive index function. A correlation existed between the monomer fluorescence intensity ratio and the solvent polarity parameter. The probes incorporated in SPMV, SPMTL, and SPMPL report a polarity value close to that of 1-hexanol $({\varepsilon}=13.29)$. In conclusion, Py-3-Py is located completely inside the membrane, not in the very hydrophobic core, but displaced toward the polar head groups of phospholipid molecules, e.g., central methylene region of aliphatic chains of phospholipid molecules.

• E2M - 전기 전자와 첨단 소재
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• 제9권3호
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• pp.265-269
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• 1996

We have studied the effect of the mesogenic core of nematic liquid crystals (NLCs) for polar (out-of-plane tilt) anchoring strength and surface order parameter on rubbed polyimide (PI) surfaces. The order of polar anchoring strength for NLCs on rubbed PI surfaces is 5CB > PCH5 > CCH5. From the above results, we suggest that the polar anchoring strength depends on the polarizability of the NLCs. The surface order parameter for NLCs is 5CB > PCH5 > CCH5 on rubbed PI surfaces. We conclude that the polar anchoring strength is strongly related to the surface order parameter on rubbed PI surfaces.

• Bulletin of the Korean Chemical Society
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• 제28권9호
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• pp.1472-1476
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• 2007

Artificial neural networks (ANNs) are successfully developed for the modeling and prediction of normalized polarity parameter (ETN) of 216 various solvents with diverse chemical structures using a quantitative-structure property relationship. ANN with architecture 5-9-1 is generated using five molecular descriptors appearing in the multi-parameter linear regression (MLR) model. The most positive charge of a hydrogen atom (q+), total charge in molecule (qt), molecular volume of solvent (Vm), dipole moment (μ) and polarizability term (πI) are input descriptors and its output is ETN. It is found that properly selected and trained neural network with 192 solvents could fairly represent the dependence of normalized polarity parameter on molecular descriptors. For evaluation of the predictive power of the generated ANN, an optimized network is applied for prediction of the ETN values of 24 solvents in the prediction set, which are not used in the optimization procedure. Correlation coefficient (R) and root mean square error (RMSE) of 0.903 and 0.0887 for prediction set by MLR model should be compared with the values of 0.985 and 0.0375 by ANN model. These improvements are due to the fact that the ETN of solvents shows non-linear correlations with the molecular descriptors.

• 대한화학회지
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• 제27권1호
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• pp.1-8
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• 1983

단일양성자성용매(메탄올, 에탄올, 1-프로판올)와 단일반양성자성용매(아세톤, 아세토니트릴, 아세토페논, 니트로벤젠) 및 이성분혼합용매계(메탄올-아세톤, 메탄올-아세토니트릴, 메탄올-벤젠)에서 염화나프탈렌술포닐과 피리딘의 친핵성치환반응에 미치는 용매효과를 전기전도도법으로 연구하였다. 단일양성자성용매의 반응속도상수는 유전상수가 큰 쪽에서 크게 관측되었고 반양성자성 용매의 반응속도상수는 유전상수가 큰 쪽에서 작게 나타났다. 아세토니트릴은 유전상수가 큰 반양성자성용매인데도 다른 반양성자성용매들보다 속도상수가 크게 관측되었다. 본 친핵성치환반응에서 용매효과는 ${\pi}^{\ast}$가 중요하고 염소이온의 이탈효과보다 수소결합형성이 전이상태를 안정화시키는데 기여함을 알 수 있었다.

• 한국세라믹학회지
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• 제37권3호
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• pp.240-246
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• 2000

The microwave dielectric properties of the complex perovskite (Pb0.5Ca0.5)(Fe0.5Ta0.5)O3 ceramics were investigated with the porosity and the dielectric mixing rule. Assuming that the specimens were mixtures of real dielectrics and pores, with 3-0 connectivity, the ionic polarizabilities modified by Maxwell's equation were more close to the theoretical values rather than those modified by Wiener's equation in porous specimens. The theoretical dielectirc loss were obtained with the infrared reflectivity spectra from 50 to 4000cm-1, which were calculated by Kramers-Kronig analysis and classical osciallator model. The relative tendency of dielectric loss calculated from the theoretical value and Maxwell's equation in the specimens with different porosities was in good agreement with the one by the post resonant method.

• 한국식품영양학회지
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• 제8권3호
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• pp.172-183
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• 1995

The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.

• Elastomers and Composites
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• 제43권4호
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• pp.230-240
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• 2008

분산중합법에 의해 무기물을 포함하는 고분자 미립자를 합성하기 위해 styrene과 n-butyl methacrylate가 알루미나와 함께 중합되었다. Styrene과 n-butylmethacrylate의 무게 비는 3:1이었고, 입자안정제는 poly(N-vinyl pyrrolidon), 중합 개시제로는 2,2'-azobis(isobutyronitrile)를 사용하여 개시제의 농도, 분산매의 종류, 분산매의 혼합 용해도 상수 (${\delta}_{mix}$), 커플링제의 종류와 농도에 따른 입자경을 조사하였다. 개시제의 농도가 증가함에 따라 입자경이 소폭 상승하였고 분산매의 극성이 증가할수록 입경이 증가하였고, 분산매로서, 이소프로판올과 이온교환수를 조성비에 따라 사용한 경우, $[{\delta}_{mix}]^{-4.01}\;{\propto}$ 평균 입자경과 $[{\delta]_{mix}]^{-0.83}\;{\propto}$ 입경 분포의 관계를 얻을 수 있었다. 커플링제의 종류와 농도변화에 따른 입자경 및 입자경 분포는 뚜렷한 차이가 없었다.