• Environmental Engineering Research
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• 제24권4호
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• pp.608-617
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• 2019

The adsorption of sulfamethoxazole (SMX) onto a NaOH-activated pine wood-derived biochar was investigated via batch experiments and models. Surprisingly, the maximum adsorption capacity of activated biochar for SMX (397.29 mg/g) was superior than those of pristine biochars from various feedstock, but comparable to those of commercially available activated carbons. Elovich kinetic and Freundlich isotherm models revealed the best fitted ones for the adsorption of SMX onto the activated biochar indicating chemisorptive interaction occurred on surface of the activated biochar. In addition, the intraparticle diffusion limitation was thought to be the major barrier for the adsorption of SMX on the activated biochar. The main mechanisms for the activated biochar would include hydrophobic, π-π interactions and hydrogen bonding. This was consistent with the changes in physicochemical properties of the activated biochar (e.g., increase in sp² and surface area, but decrease in the ratios of O/C and H/C).

• 공업화학
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• 제9권2호
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• pp.207-213
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• 1998

전편의 연구결과[1]를 토대로 또 다른 방법으로써 폴리이미드의 구조를 변화시켜 방향족 폴리벤즈이미다졸(PBI)과의 블렌드들의 상용성 및 상용성을 가져다 주는 상호작용의 세기를 상대적으로 비교하였다. 이 연구에서 방향족 폴리이미드(PI)는 두 개의 디아민인 4,4'-methylene dianiline (4,4'-MDA)과 4,4'-oxydianiline (4,4'-ODA)을 dianhydride인 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA)와의 축합반응을 통하여 용매인 DMAc로 폴리아믹산(PAA)을 합성한 후 열경화하여 얻었다. 이들 폴리아믹산(PAA)을 poly2,2-(m-phenylene)-5,5'-bibenzimidazole (PBI)와 용액 블렌딩하여 PBI/PAA 블렌드를 열경화시켜 PBI/PI의 블렌드로 전환시킨후 상용성을 조사하고 전편의 블렌드에 사용된 폴리이미드[1]와 이 연구에 사용된 폴리이미드의 구조변화에 대한 상호작용의 상대적인 크기를 조사하였다. 연구에 사용된 두 가지 블렌드인 PBI/DSDA+4.4'-MDA (Blend-V)와 PBI/DSDA+4.4'-ODA (Blend-VI)는 사용성을 보였다. 이는 성현된 필름이 투명하고, 전 블렌드 조성에 대해서 하나의 $T_g$를 가지며, 또한 블렌드 조성에 따른 N-H ($3418cm^{-1}$)와 C=O 스트레칭 밴드(1730 및 $1780cm^{-1}$)의 주파수 이동폭이 각각 $39{\sim}40cm^{-1}$, $5{\sim}6cm^{-1}$와 $3{\sim}4cm^{-1}$이었다. 이 연구에 사용된 블렌드들에 대하여 두 성분 고분자간 상호작용의 세기를 실험치와 Fox식으로 계산된 유리전이온도차로 생긴 면적(A), Gordon-Taylor 식에서의 ${\kappa}$ 값, 그리고 관능기인 N-H와 카보닐기의 주파수 이동폭의 변화로 살펴보았다. 이들에 대한 결과로 먼저, 면적 (A)와 ${\kappa}$ 값에 있어서 Blend-V와 Blend-VI이 전편의 블렌드 [1]인 Blend-III와 Blend-IV에 비해 작은 값을 보였다. 또한 관능기의 주파수 이동에 있어서도 이에 대한 결과와 유사한 결과를 보였다. 따라서 블렌드에 사용된 PI의 구조변화에 따라 상호작용이 다른 것은 PI 합성시에 사용된 서로 다른 dianhydride의 구조에서 페닐링 사이에 존재하는 linkage인 C=O보다 $SO_2$가 존재할 때[Fig. 2] 블렌드를 이루는 두 고분자사이의 상호작용인 수소결합력을 약화시키는 spacer로 작용한 것으로 사료된다. 다시 말하면, 전자가 후자보다 더 큰 입체장애를 일으켰기 때문이라 사려된다.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.196-200
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• 1986

The solvent change and salt do not affect the fluorescence quantum yield of 1,3-dimethylnaphtho[1,2-e]uracil indicating the considerable energy gap between the lowest singlet $({\pi},\;{\pi}^{\ast})\;and\;(n,\;{\pi}^{\ast})$ states in the compound. The results are consistent with the strong quenching of fluorescence by ethyl iodide. Fluorescence quantum yield is nearly independent of temperature, probably due to the relatively inefficient internal conversion. Unusual spectral difference is observed in isopentane and ethanol at 77K. The temperature dependence of emission in isopentane and in ethanol suggests that the increase of charge transfer character by the conformational change in isopentane leads to the structureless and red-shifted fluorescence, while in ethanol the decrease of the charge transfer character by the hydrogen bonding interaction results in the structured and blue-shifted fluorescence along with phosphorescence at the low temperature. Temperature dependence of emission in poly(methylmethacrylate) matrix indicates that $T_1{\to}S_0$ radiationless decay is an important process responsible for the strong temperature dependence of phosphorescence.

• Bulletin of the Korean Chemical Society
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• 제33권4호
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• pp.1259-1263
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• 2012

Two metal compounds, $[Co(phen)_2(H_2O)_2]{\cdot}2H_2SIP{\cdot}2H_2O$ 1 and $[Ni(phen)_3]{\cdot}2H_2SIP{\cdot}3H_2O$ 2, have been obtained by incorporating 1,10-phenanthroline (phen) and 5-sulfoisophthalic acid monosodium salt ($NaH_2SIP$) ligands under hydrothermal conditions. Meanwhile, the two compounds were characterized by element analysis, IR, XRD, TG-DTA and single-crystal X-ray diffraction. Both 1 and 2 present 3D supramolecular structures via O-H${\cdots}$O hydrogen bond interactions. Luminescent properties for 1 and 2 were also studied. The compound 1 has two fluorescence emission peaks centered at 398 nm attributed to the intraligand emission from the SIP ligand and at 438 nm assigned to the combined interaction of intraligand ${\pi}^*-{\pi}$ transitions of the phen ligand and ligand-to-metal-charge-transfer (LMCT) transitions (${\lambda}_{ex}$ = 233 nm). The compound 2 shows one emission band centered at 423 nm with a shoulder peak at 434 nm which may be originated from the intraligand ${\pi}^*-{\pi}$ transitions of the phen ligand (${\lambda}_{ex}$ = 266 nm).

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1323-1328
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• 2014

Molecular structures of the various conformational stereoisomers of 2,8,14,20-cyanophenyl pyrogallol[4]arenes 1 were optimized using the mPW1PW91 (hybrid Hartree-Fock density functional) calculation method. The total electronic and Gibbs free energies and the normal vibrational frequencies of the different structures from three major conformations (CHAIR, TABLE, and 1,2-Alternate) of the four stereoisomers [1(rccc), 1(rcct), 1(rctt), and 1(rtct)] were analyzed. The mPW1PW91/6-31G(d,p) calculations suggested that $1(rcct)_{1,2-A}$, 1(rctt)CHAIR, and $1(rtct)_{CHAIR}$ were the more stable conformations of the respective stereoisomers. Hydrogen bonding is the primary factor for the relative stabilities of the various conformational isomers, and maximizing the ${\pi}-{\pi}$ interaction between the cyanophenyl rings is the secondary factor. The calculated IR spectra of the more stable conformers [$1(rctt)_{CHAIR}$, $1(rcct)_{1,2-A}$, $1(rtct)_{CHAIR}$] were compared with the experimental IR spectrum of $1(rtct)_{CHAIR}$.

• Bulletin of the Korean Chemical Society
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• 제26권12호
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• pp.1946-1952
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• 2005

New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.

• 멤브레인
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• 제5권2호
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• pp.89-96
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• 1995

Azobenzene기를 가지는 인산형 양친매성 화합물의 기/액 계면에 있어서으 단분자막 거동이 $\pi-A$ 곡선 및 표면흡수스펙트라로 검토되었다. 분자간의 강한 수소결합력을 가지는 이 화합물들은 수면에 전개 후 즉시 결정화하여 단분자막 domain들을 형성한 회합체 흡수스펙트라를 나타내었다. 그러나 subphase의 조건(분자량이 큰 유가염의 첨가 및 pH의 상승)을 변화시킴에 의해 결정 domain 형성을 제어하는 것이 가능하였다. 한편, 금속이온 첨가는 인산령 양친매성 단분자막의 분재배향상태를 변화시켰다. 금속이온의 전하가 높을수록 ($1\leq2$ < 3 < 4 가), azobenzene기를 가지는 양친매성 화합물의 분자상태가 tilt된 배향성에 기인하는 장파장으로 이동한 흡수극대를 나타내었다. 이것은 서로 다른 전하를 가진 금속이온을 흡착시킴에 의해 단분자막의 분자배향성을 변화시켜, 단분자막의 집합상태 제어 가능성을 시사한다.

• Bulletin of the Korean Chemical Society
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• 제19권10호
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• pp.1105-1109
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• 1998

A chiral stationary phase derived from (S)-N-(3,5-dinitrobenzoyl)leucine N-phenyl N-alkyl amide (CSP 2) was applied in separating the two enantiomers of various π-basic aromatic derivatives of leucine N-propyl amide in order to evaluate π-basic aromatic groups as an effective derivatizing group for the resolution of a-amino acids. Subsequently N-(3,5-dimethoxybenzoyl) group was found to be very effective as a π-basic aromatic derivatizing group. Based on these results, N-(3,5-dimethoxybenzoyl) derivatives of various a-amino N-propyl amides, N,N-diethyl amides and esters were resolved on the CSP derived from (S)-N-(3,5-dinitrobenzoyl) leucine N-phenyl N-alkyl amide (CSP 2) and the resolution results were compared with those on the CSP derived from (S)-N-(3,5-dinitrobenzoyl)leucine N-alkyl amide (CSP 1). The enantioselectivities exerted by CSP 2 were much greater than those exerted by CSP 1. In addition, racemic N-(3,5-dimethoxybenzoyl)-a-mino N,Ndiethyl amides were resolved much better than the corresponding N-(3,5-dimethoxybenzoyl)-a-mino N-propyl amides and esters on both CSPs. Based on these results, a chiral recognition mechanism utilizing the π-π donor-acceptor interaction and the two hydrogen bondings between the CSP and the analyte was proposed.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1625-1629
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• 2011

Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3590-3594
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• 2014

Blue phosphorescent $(dfpypy)_2Ir(mppy)$, where dfpypy = 2',6'-difluoro-2,3'-bipyridine and mppy = 5-methyl-2-phenylpyridine, has been synthesized by newly developed effective method and its solid state structure and photoluminescent properties are investigated. The glass-transition and decomposition temperature of the compound appear at $160^{\circ}C$ and $360^{\circ}C$, respectively. In a crystal packing structure, there are two kinds of intermolecular interactions such as hydrogen bonding ($C-H{\cdots}F$) and edge-to-face $C-H{\cdots}{\pi}(py)$ interaction. This compound emits bright blue phosphorescence with ${\lambda}_{max}=472nm$ and quantum efficiencies of 0.23 and 0.32 in fluid and the solid state. The emission band of the compound is red-shifted by 40 nm relative to homoleptic congener, $Ir(dfpypy)_3$. The ancillary ligand in $(dfpypy)_2Ir(mppy)$ has been found to significantly destabilize HOMO energy, compared to $Ir(dfpypy)_3$, $(dfpypy)_2Ir(acac)$ and $(dfpypy)_2Ir(dpm)$, without significantly changing LUMO energy.