• Molecules and Cells
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• 제38권5호
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• pp.409-415
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• 2015

Low-barrier hydrogen bonds (LBHBs) have been proposed to have important influences on the enormous reaction rate increases achieved by many enzymes. ${\Delta}^5$-3-ketosteroi isomerase (KSI) catalyzes the allylic isomerization of ${\Delta}^5$-3-ketosteroid to its conjugated ${\Delta}^4$-isomers at a rate that approache the diffusion limit. Tyr14, a catalytic residue of KSI, has been hypothesized to form an LBHB with the oxyanion of a dienolate steroid intermediate generated during the catalysis. The unusual chemical shift of a proton at 16.8 ppm in the nuclear magnetic resonance spectrum has been attributed to an LBHB between Tyr14 $O{\eta}$ and C3-O of equilenin an intermediate analogue, in the active site of D38N KSI. This shift in the spectrum was not observed in Y30F/Y55F/D38N and Y30F/Y55F/Y115F/D38N mutant KSIs when each mutant was complexed with equilenin, suggesting that Tyr14 could not form LBHB with the intermediate analogue in these mutant KSIs. The crystal structure of Y30F/Y55F/Y115F/D38N-equilenin complex revealed that the distance between Tyr14 $O{\eta}$ and C3-O of the bound steroi was within a direct hydrogen bond. The conversion of LBHB to an ordinary hydrogen bond in the mutant KSI reduced the binding affinity for the steroid inhibitors by a factor of 8.1-11. In addition, the absence of LBHB reduced the catalytic activity by only a factor of 1.7-2. These results suggest that the amount of stabilization energy of the reaction intermediate provided by LBHB is small compared with that provided by an ordinary hydrogen bond in KSI.

• Bulletin of the Korean Chemical Society
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• 제33권9호
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• pp.2917-2924
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• 2012

Four novel metal-organic complexes $[Cd_2(IP)_2(TBZ)_2(H_2O)_2]{\cdot}(H_2O)$ (1), $[Zn_4(IP)_4(TBZ)_4]{\cdot}2(H_2O)$ (2), $[Zn_2(BTC)(TBZ)_2(CO_2H)]$ (3), [Co(PDC)(TBZ)] (4) (where IP = isophthalate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarboxylate; PDC = pyridine-3,4-dicarboxylate) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that 1, 2, and 3 are one-dimensional chain polymers, while 4 is a two-dimensional network polymer. The TBZ acts as a typical chelating ligand coordinated to the metal center in all complexes. The 1D chain architecture of 1 is constructed from isophthalates and cadmium atoms. A simultaneous presence of chelating, monodentate and bidentate coordination modes of IP ligands is observed in complex 2. In complex 3, the 16-membered rings are alternately arranged forming an infinite 1D double-chain structure. The 2D skeleton of 4 is formed by cobalt ions as nodes and PDC dianions as spacers, through coordination bonds. The hydrogen bonds and ${\pi}-{\pi}$ stacking play important roles in affecting the final structure where complexes 1 and 3 have 2D supramolecular networks, while complexes 2 and 4 have 3D supramolecular architectures.

• Journal of the Korean Wood Science and Technology
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• 제45권4호
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• pp.432-443
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• 2017

Maltodextrin and citric acid are two types of natural materials with the potential as an eco-friendly binder. Maltodextrin is a natural substance rich in hydroxyl groups and can form hydrogen bonds with lignoselulosic material, while citric acid is a polycarboxylic acid which can form an ester bond with a hydroxyl group at lignoselulosic material. The combination of maltodextrin and citric acid as a natural binder materials supposed to be increase the ester bonds formed within the particleboard. This research determined to investigate the bonding properties of a new adhesive composed of maltodextrin/citric acid for nipa frond particleboard. Maltodextrin and citric acid were dissolved in distillated water at the ratios of 100/0, 87.5/12.5, 75/25 and 0/100, and the concentration of the solution was adjusted to 50% for maltodextrin and 60% citric acid (wt%). This adhesive solution was sprayed onto the particles at 20% resin content based on the weight of oven dried particles. Particleboards with a size of $25{\times}25{\times}1cm$, a target density $800kg/m^3$ were prepared by hot-pressing at press temperatures of $180^{\circ}C$ or $200^{\circ}C$, a press time of 10 minute and board pressure 3.6 MPa. Physical and mechanical properties of particleboard were tested by a standard method (JIS A 5908). The results showed that added citric acid level in maltodextrin/citric acid composition and hot-pressing temperature had affected to the properties of particleboard. The optimum properties of the board were achieved at a pressing temperature of $180^{\circ}C$ and the addition of only 20% citric acid. The results also indicated that the peak intensity of C=O group increased and OH group decreased with the addition of citric acid and an increase in the pressing temperature, suggesting an interreaction between the hydroxyl groups from the lignocellulosic materials and carboxyl groups from citric acid to form the ester groups.

• Elastomers and Composites
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• 제52권3호
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• pp.180-186
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• 2017

In this work, the effect of low-temperature dehydration of a poly(styrene-co-styrenesulfonic acid) (PSSA) membrane was investigated by differential scanning calorimetry, fourier transform infrared spectroscopy (FT-IR), electron magnetic resonancespectroscopy (EMR), and $^1H$- and $^{13}C$ solid-state nuclear magnetic resonance spectroscopy. These analyses were performed at room temperature for powdered PSSA specimens with and without dehydration and the following key observations were made. First, FT-IR analysis showed that low-temperature dehydration not only transformed the [${SO_3}^-{\cdots}H^+$] ionic pair in the non-hydrated PSSA to an $SO_3H$ group, but also induced the formation of -C=C- double bonds in the dehydrated PSSA. Second, the ${-SO_3}^{\bullet}$ radical was unambiguously identified by EMR spectroscopy. Third, H-abstraction was detected by $^1H$ magic-angle spinning spectroscopy. Finally, an unexpected color shift from white for the non-hydrated PSSA to a yellowish brown for the dehydrated sample was observed. In order to explain these experimental results, it was proposed that the formation of the intermediate hydrogen ($H^{\bullet}$) or hydroxyl radical ($HO^{\bullet}$) species was initiated by the dehydration process. The sespecies attacked the $SO_3H$ group and the tertiary proton at the ${\alpha}-carbon$, resulting in the formation of $-SO^{\bullet}$ radicals and -C=C- double bonds, which correlated with the color shift in the dehydrated PSSA sample. The semechanisms are useful for understanding the simultaneous loss of an aromatic ring and -SO- groups in the PSSA fuel cell membrane.

• Applied Biological Chemistry
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• 제48권4호
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• pp.326-330
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• 2005

인공 DNase의 새로운 리간드 분자로 설계된 2,9-(N,N-dimethylethylenediamino)-1,10-phenanthroline(A) 및 2,9-(N,N-Dimethylethylenediaminomethyl)-1,10-phenanthroline(B)의 Cu(II) 착 화합물에 의한 2',3'-cAMP의 촉매 가수분해 반응에서 리간드 분자의 아미노기들과 2',3'-cAMP의 인산기 사이에 형성되는 분자내 4개의 수소결합들로 인하여 (A) 및 (B)의 Cu(II) 착 화합물은 2,9-dimethyl-o-phenanthroline의 Cu(II) 착 화합물에 의한 2',3'-cAMP의 촉매 가수분해 반응 속도를 7만배 이상 빠르게 촉진 할 것으로 예측되었다.

• 한국실천공학교육학회논문지
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• 제2권1호
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• pp.35-41
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• 2010

효소촉매반응은 통상적으로 반응속도가 매우 빠르고 동시에 높은 선택성을 보여 주는 특정이 있다. 단순 효소촉매 반응속도식을 보통 Michaelis-Menten식이라고 부른다. 효소의 활성을 간섭하는 화학물질을 저해제라고 하는데, 효소활성의 저해에는 가역적저해와 비가역적저해의 두 가지 형태로 나타난다. 만일 저해제가 수소결합과 같은 약한 결합으로 효소에 붙게 되면 이런 경우 효소저해는 가역적인 저해로 나타난다. 많은 효소 반응들은 그 반응으로부터 생성되는 생성물 자체에 의해서도 가역적 저해를 받게 된다. 생성물의 생성속도와 더불어 기질의 감소속도식은 비선형 미분방정식으로 나타 낼 수가 있다. 본 연구는 공학 분야의 학부교육을 목적으로 단순 효소반응속도식과 보다 더 복잡한 저해 효소반응속도식에 대한 수치해석의 결과를 보고 하고자 한다.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2086-2092
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• 2014

Two novel coordination compounds $[Cu_2(pypya)_3(H_2O)_2]{\cdot}Cl{\cdot}(H_2O)_5$ (1) and $\{[Cd(pypya)(ta)_{1/2}]{\cdot}H_2O\}_n$ (2) (Hpypya=2-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)acetic acid, $H_2ta$=terephthalic acid) were synthesized and characterized by single X-ray diffraction. Structure determination reveals that complex 1 and complex 2 crystallize in the triclinic system, with the P-1 space group. The asymmetric unit of 1 contains two Cu(II) ions, and their coordination modes are different. These units of complex 1 are linked together via hydrogen bonds and ${\pi}-{\pi}$ interactions, and the 3D structure of complex 1 was formed. Complex 2, a mononuclear Cd(II) coordination compound, has a 2D structure which was constructed via coordination bonds. TGA and fluorescence spectra analysis of complex 1 and complex 2 have also been studied. In addition, the geometry parameters of complex 1 have been optimized with the B3LYP method of density functional theory (DFT) to explain its coordination behavior. The electronic properties of the complex 1 and ligand Hpypya have been investigated based on the nature bond orbital (NBO) analysis at the B3LYP level of theory. The result verifies that the synergistic effect have occurred in the compound.

• Korean Chemical Engineering Research
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• 제58권2호
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• pp.176-183
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• 2020

이 연구에서는 작은 유기 분자 말단의 하이드록실기와 전이 금속 사이의 배위 결합을 통해 고분자와 유사하게 연결된 복합체를 제작하고, 점착 부여제를 추가하여 해당 물질의 점착제로의 사용 가능성을 확인하였다. 점착제 합성에 사용한 타닌산(tannic acid, TA)은 하이드록실기를 풍부하게 보유하고 있어 전이 금속과는 배위 결합이 가능하고 친수성 고분자와는 수소 결합이 가능하다. 위의 성질을 이용하여 타닌산과 전이 금속, 고분자 세 가지 성분을 한 번에 간단히 섞어 기판에 잘 펴지며 점착 능력을 보유한 특별한 유변 물성을 가지는 물질을 제작하였다. 합성에 사용한 전이 금속의 종류(Fe³⁺, Ti⁴⁺), 고분자의 종류, 처리 조건 등에 따른 유변 물성의 변화를 확인하는 과정을 통해 점착제로 사용하기에 가장 적합한 성분의 조합을 발견하였으며, 인체에 무해하며 높은 응집력과 접착력을 보유한 다목적 점착제로의 사용 가능성을 확인하였다.

• ETRI Journal
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• 제31권6호
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• pp.660-666
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• 2009

We investigate the effects of interfacial dielectric layers (IDLs) on the electrical properties of top-gate In-Ga-Zn-oxide (IGZO) thin film transistors (TFTs) fabricated at low temperatures below $200^{\circ}C$, using a target composition of In:Ga:Zn = 2:1:2 (atomic ratio). Using four types of TFT structures combined with such dielectric materials as $Si_3N_4$ and $Al_2O_3$, the electrical properties are analyzed. After post-annealing at $200^{\circ}C$ for 1 hour in an $O_2$ ambient, the sub-threshold swing is improved in all TFT types, which indicates a reduction of the interfacial trap sites. During negative-bias stress tests on TFTs with a $Si_3N_4$ IDL, the degradation sources are closely related to unstable bond states, such as Si-based broken bonds and hydrogen-based bonds. From constant-current stress tests of $I_d$ = 3 ${\mu}A$, an IGZO-TFT with heat-treated $Si_3N_4$ IDL shows a good stability performance, which is attributed to the compensation effect of the original charge-injection and electron-trapping behavior.

• 폴리머
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• 제37권4호
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• pp.507-512
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• 2013

수분산 폴리우레탄(waterborne polyurethane; WPU)의 물리화학적/전기적 특성을 개선하기 위하여 그래핀에 이소시아네이트기를 도입하고 in-situ 방법으로 폴리우레탄을 중합하여 그래핀/WPU 나노 복합체를 제조하였다. 본 연구의 접근 방법으로 그래핀을 2 wt%까지 그래핀/WPU 나노 복합체에 도입하면 기존 WPU에 비해 인장강도가 57%, 전기전도도는 약 $10^2$배 정도 향상되는 결과를 얻었다. 또한 단순 블렌드 방법으로 만든 그래핀/WPU 복합체와 비교하였을 때, in-situ 중합 방법으로 제조된 복합체가 상대적으로 우수한 기계적 물성과 전기 전도도를 가졌다. 이것은 전자현미경을 이용한 복합체 단면의 형태학적 분석으로부터 이소시아네이트기가 개질된 그래핀(iGO)이 in-situ 중합 방법에 기인한 WPU 매트릭스와의 공유결합과 수소결합을 통하여 균일하게 분산되었기 때문이다.