• Bulletin of the Korean Chemical Society
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• 제27권11호
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• pp.1825-1831
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• 2006

The influence of solvent viscosity on conformational dynamics of the heme-pocket, a small vacant site near the binding site of myoglobin (Mb) and hemoglobin (Hb), and playing a functionally important role by serving as a station in ligand binding and escape, was studied by probing time-resolved vibrational spectra of CO photodissociated from MbCO and HbCO in $D_2O$, 75 wt% glycerol/$D_2O$, and trehalose at 283 K. Two absorption bands ($B_1$ and $B_2$) of the sample in viscous solvents, arising from CO in the heme pocket, are very similar to those in $D_2O$. Two bands in Mb and Hb under all three solvents exhibit very similar nonexponential spectral evolution ($B_1$ band; blue shifting and broadening, $B_2$ band; narrowing with a negligible shifting), suggesting that in the present experimental time window of 100 ps, the extents of the spectral shift and narrowing is much influenced neither by the viscosity of solvent nor by the quaternary contact of Hb. Spectral evolution can be described by a biexponential function with a fast universal time constant of 0.52 ps and a slow time constant ranging from 13 to 32 ps. For both proteins in all three solvents majority of spectral evolution occurs with the fast universal time constant. The magnitude of the slow rate in the spectral shift of B1 band decreases with increasing solvent viscosity, indicating that it is influenced by global conformational change which is retarded in viscous solvent, thereby serve as a reporter of global conformational change of heme proteins after deligation.

• Macromolecular Research
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• 제12권3호
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• pp.322-324
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• 2004

Poly(1-dodecyl-2,5-pyrrylene vinylene) (PDPV) has an extended 1t-conjugated structure and exhibits characteristic spectroscopic features. The PDPV we prepared has an absorption maximum at 510nm and its long absorption tail at ca. 750nm in methylene chloride is due to the long 1t-conjugated system connected to vinyl group. The large red-shift of emission was 625nm upon excitation at 480nm, which suggests the existence of a low emissive state. The emission of PDPV in less-polar solvents decreased markedly relative to that in the more-polar solvents; this observation was ascribed possibly to quenching by a strong vibrational mode of the dodecyl groups of PDPV in less-polar solvents. Furthermore, the emission from the high-energy side had a single decay component (0.1㎱, 49.96%), while that from the low-energy side had two components (0.6㎱, 27.1 %; 2.7㎱, 22.87%). We characterized the redox properties of PDPV by cyclic voltammetry. Every redox peak showed irreversible behavior; the oxidation peaks appeared at 1.7,0.8, and 0.6V and the reduction peak at -0.5V.

• BMB Reports
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• 제38권2호
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• pp.198-205
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• 2005

Resveratrol (RES) and genistein (GEN) are the dietary natural products known to possess chemopreventive property and also the ability to repair DNA damage induced by mutagens/carcinogens. It is believed that the therapeutic activity of these compounds could be primarily due to their interaction with nucleic acids but detailed reports are not available. We here explore the interaction of these drugs with nucleic acids considering DNA and RNA as a potential therapeutic target. The interaction of RES and GEN has been analysed in buffered solution with DNA [saline sodium citrate (SSC)] and RNA [tris ethylene diammine tetra acetic acid (TE)] using UV-absorption and Fourier transform infrared (FTIR) spectroscopy. The UV analysis revealed lesser binding affinity with nucleic acids at lower concentration of RES (P/D = 5.00 and 10.00), while at higher drug concentration (P/D = 0.75, 1.00 and 2.50) hyperchromic effect with shift in the ${\lambda}_{max}$ is noted for DNA and RNA. A major RES-nucleic acids complexes was observed through base pairs and phosphate backbone groups with K = $35.782\;M^{-1}$ and K = $34.25\;M^{-1}$ for DNA-RES and RNA-RES complexes respectively. At various concentrations of GEN (P/D = 0.25, 0.50, 0.75, 1.00 and 2.50) hyperchromicity with shift in the ${\lambda}_{max}$ from 260 $\rightarrow$ 263 om and 260 $\rightarrow$ 270 nm is observed for DNA-GEN and RNA-GEN complexes respectively. The binding constant (from UV analysis) for GEN-nucleic acids complexes could not be obtained due to GEN absorbance overlap with that of nucleic acids at 260 nm. Nevertheless a detailed analysis with regard to the interaction of these drugs (RES/GEN) with DNA and RNA could feasibly be understood by FTIR spectroscopy. The NH band of free DNA and RNA which appeared at $3550-3100\;cm^{-1}$ and $3650-2700\;cm^{-1}$ shifted to $3450-2950\;cm^{-1}$ and $3550-3000\;cm^{-1}$ in DNA-RES and RNA-RES complexes respectively. Similarly shifts corresponding to $3650-3100\;cm^{-1}$ and $3420-3000\;cm^{-1}$ have been observed in DNA-GEN and RNA-GEN complexes respectively. The observed reduction in NH band of free nucleic acids upon complexation of these drugs is an indication of the involvement of the hydroxyl (OH) and imino (NH) group during the interaction of the drugs and nucleic acids (DNA/RNA) through H-bonded formation. The interaction of RES and GEN with bases appears in the order of G $\geq$ T > C > A and A > C $\geq$ T > G. Further interaction of these natural compounds with DNA and RNA is also supported by changes in the vibrational frequency (shift/intensity) in symmetrical and asymmetrical stretching of aromatic rings of drugs in the complex spectra. No appreciable shift is observed in the DNA and RNA marker bands, indicating that the B-DNA form and A-family conformation of RNA are not altered during their interaction with RES and GEN.

• 보존과학회지
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• 제37권6호
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• pp.648-658
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• 2021

본 연구에서는 증해제 종류(천연 잿물, Na₂CO₃)와 초지 시기(겨울, 여름)가 다른 한지를 선정하여 105℃의 가속열화 환경에서 나타나는 한지의 화학적 변화를 분석하고자 하였다. 백색도(brightness) 및 황색도(yellowness), pH를 측정하여 한지의 열화 정도를 확인하였으며, 적외선 분광분석(FT-IR)을 통해 열화가 진행됨에 따른 셀룰로오스 내 작용기의 변화 정도를 나타내었다. 이를 바탕으로 X선 회절분석(XRD)과 라만 분광분석을 실시하여 FT-IR에서 나타난 셀룰로오스 내 결정 및 비결정영역의 변화를 검증하였다. FT-IR 분석결과, 열화가 진행됨에 따라 셀룰로오스 내 비결정영역의 흡광도는 감소하는 반면 결정영역의 흡광도는 미미하게 증가하는 양상을 보였다. 결정영역의 증가는 XRD 분석 후 결정화도(Crystallinity Index, CI) 산출을 통해 열화 후 다소 증가함을 보여 같은 경향을 띠는 것을 확인할 수 있었다. 또한 라만 분광분석 결과, 열화 후 측정된 형광을 통해 초지 조건에 따른 셀룰로오스 내 비결정영역의 분해 정도를 확인하였다.

• 공업화학
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• 제9권1호
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• pp.76-81
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• 1998

초임계 $CO_2$중에 미량 희석된 아세톤의 실리카겔(SG800, 세공경 80nm, 입자경 $10{\mu}m$)표면에서의 물리적인 흡착현상을 FTIR 측정기법에 의해 측정하여, 그 결과를 크로마토그래피 측정기법을 이용해 얻어진 흡착현상과 비교하였다. 크로마토 측정기법에 의해 얻어진 흡착등온선(온도 313K, 압력 1MPa~15MPa)은 $CO_2$의 임계압력(7.28MPa) 보다 낮은 압력에서 최대값을 가지며, 압력이 증가함에 따라 감소하는 경향을 보여준다. 이 결과는 아세톤과의 수소결합 형성에 의해 적색변위(red-shift, 흡착피크가 낮은 파수 영역으로 이동하는 현상)한 실리카겔 표면 OH기의 IA(Integral Absorbance, 적분강도)의 압력의존성과 정성적으로 일치한다. 그러나 초임계유체 영역에서의 크로마토 측정기법에 의한 흡착등온선의 압력증가에 따른 감소비가 FTIR 측정기법에 의한 IA 곡선의 압력증가에 따른 감소비에 비해 조금 크게 감소하는 경향을 보여준다. 이 결과는 비교적 약한 상호작용을 가지는 van der Waals 결합력과 상대적으로 강한 흡착력을 가지는 수소결합력이 실리카겔 표면에서의 아세톤의 흡착에 동시에 영향을 미치고 있다는 것을 나타낸다. 초임계 $CO_2$와 $N_2$가스중에 미량 희석된 트리에틸아민의 FTIR 실험결과로부터 실리카겔 표면에 흡착된 아민류 유기용매의 독특한 분광학적 흡착특성, 흡착띠(band)가 $1300cm^{-1}$ 부근까지 적색변위하는 특성을 발견할 수 있었다.

• 대한화학회지
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• 제17권2호
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• pp.85-94
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• 1973

니트로 벤젠의 세가지 유도체, 즉 1.3.5-트리니트로벤젠(1.3.5-TNB), m-디니트로벤젠(m-DNB) 및 니트로벤젠(NB)등이 11종의 염기성 유기 용매 즉, ${\alpha}$-피콜린, 피리딘, 디메틸술포옥시드(DMSO), NN′-디메틸초산아미드(NN′-DMA), 테트라히드로퓨란(THF), 1,4-디옥산, 디에틸에테르, 시안화메틸, 프로필렌옥시드, 에피클로로히드린, 초산메틸등과 사염화탄소용액중에서 전하전이착물을 형성함을 자외선분광광도법에 의해 확인하고, 이들 전하전이착물의 안정도 상수를 결정하였다. Drago 와 Wayland 의 이중척도엔탈피식(double-scale-enthalpy)을 수정하여 $logK = E_AC_A+E_DC_D$식을 얻고, 이것을 써서 정전기적효과 $E_D$와 공유성효과 $C_D$값을 11종의 유기 용매에 대해 얻었다. 이 두 효과는 전하전이착물의 안정도 상수 K와 그리고 적외선 흡수 스펙트럼의 신축진동수변화 ${\Delta}{\nu}_C=O$에 영향을 주며, 특히 $C_D$ sms 안정도 상수에 비례하였고, 신축진동수변화 ${\Delta}{\nu}_{C=O}= 37.4-5.47E_D+12.1C_D$의 실험식을 얻었다. ${\pi}$결합을 가진 분자들이 전이착물을 이룰 때 정전기적효과와 공유성효과와 공유성효과가 모두 관여하며, 그밖에 결합하는 분자의 ${\pi}$궤도함수도 중요한 역할을 한다는 것을 알았다.