• BMB Reports
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• v.40 no.6
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• pp.1090-1094
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• 2007

Melittin (ME), a linear 26-residue non-cell-selective antimicrobial peptide, displays strong lytic activity against bacterial and human red blood cells. To design ME analogue with improved cell selectivity, we synthesized a melittin diastereomer (ME-D) with D-amino acid in the leucine zipper sequence (Leu-6, Lue-13 and Ile-20). Compared to ME, ME-D exhibited the same or 2-fold higher antibacterial activity but 8-fold less hemolytic activity. Circular dichroism analysis revealed that ME-D has much less $\alpha$-helical content in $\alpha$-helical content in the presence of zwitterionic EYPC/cholesterol (10 : 1, w/w) liposomes compared to negatively charged EYPE/EYPG (7 : 3, w/w) liposomes. The blue shift of the fluorescence emission maximum of ME-D in zwitterionic EYPC/cholesterol (10 : 1, w/w) liposomes was much smaller than in negatively charged EYPE/EYPG (7 : 3, w/w) liposomes. These results suggested that the improvement in therapeutic index/cell selectivity of ME-D is correlated with its less permeability to zwitterionic membranes.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3658-3662
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• 2010

A new bis-Ru(II) complex, in which two [Ru(1,10-phenanthroline)$_2$dipyrido[3,2-a:2',3'-c]phenazine]$^{2+}$ were tethered by a 1,3-bis(4-pyridyl)propane linker, was synthesized and its binding mode and stoichiometry to DNA was investigated by optical spectroscopy including linear dichroism (LD) and fluorescence intensity measurement. The magnitude of the negatively reduced LD signal of the bis-Ru(II) complex in the dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) ligand absorption region appeared to be similar compared to that in the DNA absorption region, which is considered to be a diagnostic for DPPZ ligand intercalation. The binding stoichiometry measured from its LD magnitude and enhanced fluorescence intensity corresponds to one ligand per three DNA bases, effectively violating the nearest neighbouring site exclusion model for classical DNA intercalation. This observation is in contrast with monomer analogue [Ru(1,10-phenanthroline)$_2$dipyrido[3,2-a:2',3'-c]phenazine]$^{2+}$, which is saturated at the DPPZ ligand to DNA base ratio of 0.25, or one DPPZ ligand per four nucleobases.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2117-2124
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• 2013

The binding properties and sequence selectivities of ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with $poly[d(A-T)_2]$ and $poly[d(G-C)_2]$ were investigated using conventional spectroscopic methods. When bound to $poly[d(A-T)_2]$, a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of $poly[d(A-T)_2]$. These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of $45^{\circ}$ between the molecular plane of the bridging moiety of the ${\Delta}{\Delta}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex and the local DNA helix axis calculated from reduced linear dichroism ($LD^r$) spectrum further supported the minor groove binding mode. In the case of ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex, this angle was $55^{\circ}$, suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the $poly[d(A-T)_2]$. In contrast, neither ${\Delta}{\Delta}$-nor ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex produced significant CD or $LD^r$ signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes were partially accessible to the $I^-$ quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to $poly[d(G-C)_2]$. These observations suggest that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes bind at the surface of $poly[d(G-C)_2]$, probably electrostatically to phosphate group. The results indicate that ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ are able to discriminate between AT and GC base pairs.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1314-1318
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• 2010

The $[Ru(tpy)_2]Cl_2$ (tpy:2,2':6',2"-terpyridine) complex was synthesized and its structure was confirmed by $^1H$-NMR and elemental analysis. Its binding mode toward DNA was compared with the well-known $[Ru(bpy)_3]Cl_2$ (bpy:2,2-bipyridyl), using isotropic absorption, linear dichroism(LD) spectroscopy, and an energy minimization study. Compared to $[Ru(bpy)_3]^{2+}$, the $[Ru(tpy)_2]^{2+}$ complex exhibited very little change in its absorption pattern, especially in the MLCT band, upon binding to DNA. Furthermore, upon DNA binding, both Ru(II) complexes induced a decrease in the LD magnitude in the DNA absorption region. The $[Ru(tpy)_2]^{2+}$ complex produced a strong positive LD signal in the ligand absorption region, which is in contrast with the $[Ru(bpy)_3]^{2+}$ complex. Observed spectral properties led to the conclusion that the interaction between the ligands and DNA bases is negligible for the $[Ru(tpy)_2]^{2+}$ complex, although it formed an adduct with DNA. This conclusion implies that both complexes bind to the surface of DNA, most likely to negatively charged phosphate groups via a simple electrostatic interaction, thereby orienting to exhibit the LD signal. The energy minimization calculation also supported this conclusion.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.304-304
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• 2011

We investigated the effect of different spin direction of anti-ferromagnetic layer on the magnetic properties of ferromagnetic layer in Fe-NiO and Fe-CoO bi-layer systems. For Fe-NiO system, we prepared the clean MgO(001) surface half-covered with 20 nm Ag films as a substrate for magnetic layers. Then we grew NiO wedge layers on the substrate, and added 8 monolayer(ML) Fe layers on the wedge layer. We examined magnetic properties of the bi-layer system using the surface magnetic optical Kerr effect(SMOKE) and X-ray magnetic linear dichroism(XMLD). From SMOKE measurement we observed the coercivity enhancement due to the set-up of anti-ferromagnetic order of NiO films in both of the Fe/NiO/MgO(001) and Fe/NiO/Ag/MgO(001) system. The most remarkable results in our observation is that the coercivity enhancement of Fe/NiO/Ag/MgO(001) is much larger than that of Fe/NiO/MgO(001). XMLD experiments confirmed the out-of-plane spin direction of NiO layers in Fe/NiO/MgO(001) and in-plane spin-direction of NiO layers in Fe/NiO/Ag/MgO(001), and we concluded that the origin of large enhancement of coercivity is due to the strong parallel coupling between Fe layers and NiO layers. We also confirmed that this strong parallel coupling maintained across the thin Ag layer inserted between Fe and NiO layers. For Fe-CoO system, we prepared Fe/CoO/Ag(001) and Fe/CoO/MnO(001) systems and observed much larger coercivity enhancement in Fe/CoO/Ag(001).

• 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.

• Bulletin of the Korean Chemical Society
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• v.33 no.4
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• pp.1165-1169
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• 2012

The fluorescence intensity of DNA-intercalated ethidium with [ethidium]/[DNA base] being 0.005 was quenched upon the binding of another intercalating ligand, meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP). Addition of $Ca^{2+}$ enhanced the quenching efficiency. The range of separations between donor and acceptor molecules, within which total quenching occurs, was calculated using a one-dimensional resonance energy transfer mechanism to be 9.5 base-pairs or $32.3{\AA}$ in the absence of $Ca^{2+}$ ions. The distance increased to 18.7 base-pairs or about $63.6{\AA}$ in the presence $100{\mu}M$ $Ca^{2+}$. Considering that (1) $Ca^{2+}$ had little effect on the binding modes of ethidium and TMPyP, which was investigated by reduced linear dichroism and (2) spectral overlap between the emission spectrum of ethidium and the absorption spectrum of TMPyP was maintained in the presence of $Ca^{2+}$, contributions from orientation factor and spectral overlap to $Ca^{2+}$-induced enhancement in DNA mediated energy transfer was limited. Although there is no direct evidence, electron transfer along the DNA stem may accompany the observed fluorescence quenching. In this respect, DNA bound $Ca^{2+}$ act as a partially conducting medium.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 1998.02a
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• pp.17-17
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• 1998

Synchrotron radiation is produced when charged particles moving with relativistic velocities a are accelerated - for example, deflected by the bending magnets which guide the electron or p positrons in circular accelerators or storage rings. By using special focusing magnetic lattices i in the particle accelerators it is possible to make the dimensions of the particle beam very small with a hi맹 charge density which results in a light source with high b디lIiance. Synchrotron light h has important properties which make it ideal for a wide range of investigations in surface s science. The fact that the spectrum of electromagnetic radiation emitted in a bending magnet e extends in a continuum from the 얹r infra red region to hard x-rays means that it is id않I for a v variety of spectroscopic studies. Since there are no convenient lasers, or other really bright l light sources, in the vacuum ultraviolet and soft x-ray re.밍ons the development of synchrotron r radiation has enabled enormous advances to be made in this di펌C비t spectr따 re밍on. P Polarization-dependent measurements, for ex없nple ellipsometry or circular dichroism studies a are possible because the radiation has a well-defined polarization - linear in the plane of orbit w with additional right-circular, or left-circular, components for emission an생es above, or below, t the horizontal, respectively. Since the synchrotron light is emitted from a bunch of charge c circulating in a ring the light is emitted with a well-defined time structure with a short flash of l light every time a bunch passes an exit port. The time structure depends on the size of the ring a and the number and sequence of filling of the bunches. A pulsed light source enables time¬r resolved studies to be performed which provide direct information on the lifetimes and decay m modes of excited states and in addition opens up the possibility of using time of flight t techniques for spectroscopic studies. The fact that synchrotron radiation is produced in a clean u ultrahi야 vacuum environment is of gr않t importance for surce science studies. The current t비rd generation synchrotron light sources provide exceptionally high baliance and stability a and open up possibilities for experiments which would have been inconceivable only a short time ago.