• Title/Summary/Keyword: Polarized spectroscopy

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Interaction of Cu(II)-meso-tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4) with Native and Synthetic Polynucleotides Probed by Polarized Spectroscopy

  • Lee, Mi-Jin;Lee, Gil-Jun;Lee, Dong-Jin;Kim, Seog-K.;Kim, Jong-Moon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1728-1734
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    • 2005
  • The interactions of Cu(II)-meso-Tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4), respectively referred to as o-, m- and p-CuTMPyP, and DNA, poly$[d(A-T)_2]$ and poly$[d(G-C)_2]$ were investigated by circular and linear dichroism (CD and LD). In the o-CuTMPyP case, in which the rotation of the pyridinium ring is prevented, the shape of the CD spectrum when associated to DNA and poly$[d(A-T)_2]$ resembles and is characterized by a positive band at a low drug to DNA concentration ratio (R ratio) and is bisignate at a high R ratio. The former CD spectrum shape has been attributed to porphyrin that is bound monomerically outside of DNA while the latter can be attributed to those that are stacked. When o-CuTMPyP is bound to poly$[d(G-C)_2]$, the excitonic CD appeared at a relatively high R ratio. In contrast, a characteristic negative CD band in the Soret region was apparent for both m- and p-CuTMPyP when bound to DNA and poly$[d(G-C)_2]$ at the low R ratios, indicating that the porphyrin molecule intercalates. However, the DNA is bent near the intercalation site and the plane of the porphyrin molecule tilts relative to the DNA helix axis, as judged by the magnitude of the reduced LD. Various stacking patterns were identified by the shape of the CD spectrum for m- and p-CuTMPyP when bound to poly$[d(A-T)_2]$. Three species for the former complex and two for the latter complex were found which may reflect the extent of the stacking.

LC Alignment Behaviors at Rubbed Films of Brush Polyimides;Perpendicular LC Alignment versus Parallel LC Alignment

  • Lee, Taek-Joon;Hahm, Seok-Gyu;Lee, Seung-Woo;Chae, Bok-Nam;Lee, Seong-June;Kim, Seung-Bin;Jung, Jin-Chul;Ree, Moon-Hor
    • 한국정보디스플레이학회:학술대회논문집
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    • 2004.08a
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    • pp.766-768
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    • 2004
  • Rubbed films of a series of poly(p-phenylene 3,6-bis(4-(n-alkyloxy)phenyloxy)pyromellitimide)s (Cn-PMDA-PDA PIs), which are well-defined brush PIs composed of two aromatic-aliphatic bristles per repeat unit of a fully rodlike backbone, were investigated in detail using atomic force microscopy (AFM), optical retardation analysis and linearly polarized infrared (IR) spectroscopy in order to elucidate their surface morphology and molecular orientation. The liquid crystal (LC) alignment behavior and the anchoring energy of LC molecules on the rubbed films were also determined.

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Study on Applying Techniques of Wooden Lacquerware Artifacts Excavated from Imdang-dong Site, Gyeongsan, Korea (경산 임당 유적 출토 칠기유물의 칠기법 연구)

  • Lee, Kwang-Hee;Han, Gyu-Seong
    • Journal of Conservation Science
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    • v.33 no.2
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    • pp.61-73
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    • 2017
  • In order to identify the application techniques of wooden lacquerware artifacts, optical/polarized light microscopy, Fourier transform infrared (FT-IR) spectroscopy, and scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysis (EDX) were conducted on the lacquer films of 61 wooden lacquerware artifacts excavated from the Imdang-dong site, Gyeongsan, Korea. Powdered soil, soot, and charcoal were used as a filler for the undercoat, and iron oxide ($Fe_2O_3$) was used as a red pigment. Five different applying techniques were identified for the undercoat according to the composition of the lacquer. Eight different application techniques were identified for the final coat (on the middle layer and surface layer). Totally seventeen application techniques were identified based on the combination methods of the undercoat and finalcoat. Consequently, the undercoating techniques of Imdang-dong lacquerwares were found to be similar to those of lacquerwares from excavated in other provinces. However, the use of iron oxide as a red pigment at Gyeongsang province is very characteristic compared with others.

Unusual Alignment of Liquid Crystals on Rubbed Films of Polyimides with Fluorenyl Side Groups

  • Hahm, Suk-Gyu;Lee, Taek-Joon;Chang, Tai-Hyun;Jung, Jin-Chul;Zin, Wang-Cheol;Ree, Moon-Hor
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.239-239
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    • 2006
  • In the present study, we synthesized CBDA-FDA and its analogue, poly(4,4' -(9,9-fluorenyl)diphenylene pyromellitimide) (PMDA-FDA), and then investigated quantitatively the orientational distributions of the polymer chain segments in the surfaces of their films by using linearly polarized Fourier transform infrared (FTIR) spectroscopy and optical retardation analysis. We also examined the films' surface topographies using high spatial resolution atomic force microscopy (AFM). Further, rubbed films were used to assemble antiparallel and $90^{\circ}-twisted$ nematic (TN) LC cells, and the alignment behaviors, pretilt angles and anchoring energies of the LC molecules in the cells were determined. The films were found to have very interesting surface morphologies and LC alignment behaviors, which have not previously been reported. The observed LC alignments, pretilt angles and anchoring energies are discussed by taking into account the interactions of the LC molecules with the oriented polymer chain segments and the surface morphologies.

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DNA Mediated Energy Transfer from 4',6-Diamidino-2-phenylindole to Ru(II)[(1,10-phenanthroline)2L]2+ : Effect of Ligand Structure

  • Youn, Mi-Ryung;Moon, Seok-Joon;Lee, Bae-Wook;Lee, Dong-Jin;Kim, Jong-Moon;Kim, Seog-K.;Lee, Chong-Soon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.537-542
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    • 2005
  • It was proposed that Ru(II)[(1,10-phenanthroline)$_2$dipyrido[3,2-a:2',3'-c]phenazine ([Ru(phen)$_2$DPPZ]$^{2+}$)complexes and 4',6-diamidino-2-phenylindole (DAPI) simultaneously bind to poly[d(A-T)$_2$] (Biophysics. J. 2003, 85, 3865). Förster type resonance energy transfer from excited DAPI to [Ru(phen)2DPPZ]$^{2+}$ complexes was observed. In this study, we synthesized $\Delta$- and $\wedge$-[Ru(phenanthroline)$_2$dipyrido[3,2-a:2’3’c]6-azaphenazine] ([Ru(phen)$_2$DPAPZ]$^{2+}$) at which the DNA intercalating ligand DPPZ was replaced and we studied its binding properties to poly[d(A-T)$_2$] in the presence and absence of DAPI using polarized spectroscopy and fluorescence techniques. All the spectroscopic properties of the [Ru(phen)$_2$DPAPZ]$^{2+}$-poly[d(A-T)$_2$] complex were the same in the presence and absence of DAPI that blocks the minor groove of polynucleotide, suggesting both $\Delta$- and $\wedge$-[Ru(phen)$_2$DPAPZ]$^{2+}$ complexes are located at the major groove of poly[d(A-T)2]. On the other hand, in contrast with [Ru(phen)$_2$DPPZ]$^{2+}$, both $\Delta$- and $\wedge$-[Ru(phen)$_2$DPAPZ]$^{2+}$ exhibited almost twice the efficiency in the fluorescence quenching of DAPI that binds at the minor groove of poly[d(A-T)$_2$]. This observation indicates that the efficiency of the Förster type resonance energy transfer can be controlled by a small change in the chemical structure of the intercalated ligand.

Crystal Structure and Tautomerism Study of the Mono-protonated Metformin Salt

  • Wei, Xiaodan;Fan, Yuhua;Bi, Caifeng;Yan, Xingchen;Zhang, Xia;Li, Xin
    • Bulletin of the Korean Chemical Society
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    • v.35 no.12
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    • pp.3495-3501
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    • 2014
  • A novel crystal, the mono-protonated metformin acetate (1), was obtained and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. It was found that one of the imino group in the metformin cation was protonated along with the proton transfer from the secondary amino group to the other imino group. Its crystal structure was then compared with the previously reported diprotonated metformin oxalate (2). The difference between them is that the mono-protonated metformin cations can be linked by hydrogen bonding to form dimers while the diprotonated metformin cations cannot. Both of them are stabilized by intermolecular hydrogen bonds to assemble a 3-D supermolecular structure. The four potential tautomer of the mono-protonated metformin cation (tautomers 1a, 1b, 1c and 1d) were optimized and their single point energies were calculated by Density Functional Theory (DFT) B3LYP method based on the Polarized Continuum Model (PCM) in water, which shows that the most likely existed tautomer in human cells is the same in the crystal structure. Based on the optimized structure, their Wiberg bond orders, Natural Population Analysis (NPA) atomic charges, molecular electrostatic potential (MEP) maps were calculated to analyze their electronic structures, which were then compared with the corresponding values of the diprotonated metformin cation (cation 2) and the neutral metformin (compound 3). Finally, the possible tautomeric mechanism of the mono-protonated metformin cation was discussed based on the observed phenomena.

Synthesis of Cholesteric Liquid Crystal and Its Application as a Polarizing Component on the Optical Film (콜레스테릭 액정의 합성과 광학필름용 편광성분으로서의 응용)

  • Kim, Yong-Suk;Lee, Kwang-Yeon;Ahn, Cheol-Heung;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.19 no.6
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    • pp.661-667
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    • 2008
  • In this study, cholesteric liquid crystal (CLC) was synthesized and applied as a polarizing component on the optical film of back light units (BLU) for LCDs. After mixing CLC with nematic liquid crystal, this mixture was fulfilled in the module consisting of two films and then its amplifying efficiency and polarizing ability for a planarly emitted light were examined to apply as a BLU polarizer film for increasing the brightness of light. The properties of CLC compound were tested by UV/Visible spectroscopy and polarizing optical microscopy (POM). Flexible spacer was made by linear carboxylic acid group of cholesteric derivatives between cholesterol mesogen units for one-axis orientation in each layer. The CLC containing film could be used as a module to increase the ability of polarization and to enhance brightness of BLU and to widen wavelength range by stacking the films.

Mineralogy of Clinopyroxene from the Geodo Mine (거도광산의 단사휘석에 관한 광물학적 연구)

  • 최진범;김수진
    • Journal of the Mineralogical Society of Korea
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    • v.2 no.1
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    • pp.26-36
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    • 1989
  • Clinopyroxene in the Geodo mine belongs to diopside-hedenbergite series. It is widely distributed throughout the mine area together with garnet and is also closely related with Fe-mineralization. Clinopyroxenes in the Geodo mine including two samples from the sangdong and Ulchin Mines are studied using polarized microscope, EPMA, XRD, and IR spectroscopy for occurrence, chemistry, structure, and crystal chemistry. Especially, variations in unit-cell parameters are examined in relation with the substitution scheme between Fe and Mg cations. Clinopyroxenes in the Geodo mine occur in both endoskarn and exoskarn zone. It is mostly anhedral to subhedral with fine- to medium-grained in texture, but some have bigger crystals of short prismatic or columnar habits. Clinopyroxene occurs as monomineralic or is associated with mostly garnet and sometimes with actinolite, magnetite, epidote, and chlorite. Chemical analysis reveals that the Geodo clinopyroxene is diopsidic in composition (Di: 65-96%). This fact is in good contrast with garnet chemistry showing mostly andraditic (An: 41-82%). Especially, clinopyroxene coexisting with magnetite belongs to nearly end member diopside (Di: 97-99%). Thus, diopside-andradite pair indicates that Geodo skarns were formed under the reduced environment. X-ray diffraction analysis shows unit-cell parameters vary with increase of Fe contents: a = 9.765-9.838$\AA$, b = 8.943-9.020$\AA$, c= 5.240-5.253$\AA$.$\beta$ = 105.70-104.83$^{\circ}$, and V =440.64-448.19$\AA$3. It is noted from the least square regression that a, b and V increase linearly with increase of Fe content, while $\beta$ slightly decreases and c remains nearly unchanged as change in Fe content. These trends are to difference between synthetic and natural clinopyroxenes. This fact is also recognized in IR spectra which show a slight shift of several absorption bands toward lower wavenumber region with increasing Fe content.

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Binding Modes of New Bis-Ru(II) Complexes to DNA: Effect of the Length of the Linker

  • Kwon, Byung-Hyang;Choi, Byung-Hoon;Lee, Hyun-Mee;Jang, Yoon-Jung;Lee, Jae-Cheol;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1615-1620
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    • 2010
  • Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

Effect of Molecular Weights of Polyethyleneimine on the Polyplex Formation with Calf Thymus DNA

  • Cho, Tae-Sub;Jungho Han;Kim, Seog K.;Lee, Jae-Cheol
    • Macromolecular Research
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    • v.12 no.3
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    • pp.276-281
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    • 2004
  • In this study we investigated the spectral properties, including electric absorption, circular and linear dichroism (CD and LD), and fluorescence emission, of DNA in a DNA-branched polyethyleneimine (BPEI) polyplex at various polymer molecular weights (M$\_$w/) and BPEI-amine-to-DNA-phosphate ratios (N/P ratios). All BPEIs exhibited a common N/P dependence in their absorption and CD spectra. At N/P ratios < 1.0, we observed some hyperchromism in the absorption spectrum, red-shifts in CD bands, and decreases in LD intensity and fluorescence intensity of intercalated ethidium. At intermediate N/P ratios, complete collapse of all spectra occurred. As the N/P ratio increased further, the polyplex dissolved in water. From its characteristic CD spectrum obtained under these conditions, we conclude that the DNA exists in a B-like form. The fluorescence and LD intensities never recovered even at high N/P ratios- which indicates that the dissolved polyplex possesses positive charges and the DNA in the polyplex is condensed despite its B-form CD spectrum. The N/P range in which the absorption and CD signals collapsed was wider when the BPEIs M$\_$w/ decreased. In the case where the BPEIs M$\_$w/ was 0.8 k, recovery of the absorption and CD spectral properties at a high N/P ratio was never achieved, which suggests that the molecular weight of the polymer plays an important role in its dissolution at a high N/P ratio.