• Textile Coloration and Finishing
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• v.25 no.4
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• pp.254-261
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• 2013

In this study, we synthesized a new fluorescent polypyridyl dye 2 containing a 2,2'-bipyridine in the center and two 2,2':6',2"-terpyridines at both ends. When exposed to various metal ions, the dye 2 showed selective fluorescence responses. In the presence of $Cu^{2+}$ and $Ni^{2+}$, it exhibited a highly effective fluorescence quenching, leading to large $K_{sv}$ values of up to $10^5$. In response to most other metal ions including $Al^{3+}$, in contrast, its fluorescence changes little, showing a small Ksv value at $10^2$. Meanwhile, the compound 2 revealed a differentiated fluorescence response to $Zn^{2+}$, which is evidenced by a large red shift of > 100 nm. Such a red shift from the ion binding is attributed to the planarization of the bipyridyl unit extending the effective conjugation length in conjunction. A polypyridyl compound will find important usefulness in chemosensor application due to its selective binding to metal ions. Subsequent research concerned with modified derivatives is currently going on, as a way to provide high solubility even after metal-complexing.

• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1633-1637
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• 2010

The UV-vis absorption spectrum of protoporphyrin IX shows a very sharp and strong absorption maximum peak at 398 nm in acetonitrile-water mixture solution (1:1 v/v). When divalent metal ions such as $Cu^{2+}$, $Zn^{2+}$, and $Ca^{2+}$ ion were added to protoporphyrin IX, metal protoporphyrin IX complexes were thereby produced. Cu-protoporphyrin IX complexes have the largest formation constant ($K_f$) among them. The fluorescence intensity of protoporphyrin IX was diminished by the presence of $Cu^{2+}$, $Zn^{2+}$, $Ca^{2+}$, $Mn^{2+}$, and $Ni^{2+}$ ions as quenchers. However, $Mg^{2+}$, $Mn^{2+}$, and $Ni^{2+}$ ions are hardly combined with protoporphyrin IX. $Mg^{2+}$ ion does not take part in the fluorescence quenching process of protoporphyrin IX in acetonitrile-water mixture solution. According to the Stern-Volmer plots, fluorescence quenching by $Cu^{2+}$, $Zn^{2+}$, and $Ca^{2+}$ ions involves static quenching, which is due to complex formation. On the contrary, dynamic quenching has a large influence on the overall quenching process, when $Mn^{2+}$ and $Ni^{2+}$ ions were added to protoporphyrin IX in acetonitrile-water mixture solution.

• Journal of the Korean Chemical Society
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• v.55 no.6
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• pp.932-935
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• 2011

Using tetrabutyl titanate as precursor, $Eu^{3+}$ doped $TiO_2$ nano-powder was prepared by sol-gel method, the nature of luminescence of nano-powder was studied. The interaction of chlorpyrifos with $Eu^{3+}$ doped $TiO_2$ was studied by absorption and fluorescence spectroscopy. The results indicated the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was quenched by chlorpyrifos and the quenching rate constant ($k_q$) was $1.24{\times}10^{11}\;L/mol{\cdot}s$ according to the Stern-Volmer equation. The dynamics of photoinduced electron transfer from chlorpyrifos to conduction band of $TiO_2$ nanoparticle was observed and the mechanism of electron transfer had been confirmed by the calculation of free energy change (${\Delta}G_{et}$) by applying Rehm-Weller equation as well as energy level diagram. A new rapid method for detection of chlorpyrifos was established according to the fluorescence intensity of $Eu^{3+}$ doped $TiO_2$ was proportional to chlorpyrifos concentration. The range of detection was $5.0{\times}10^{-10}-2.5{\times}10^{-7}mol/L$ and the election limit ($3{\sigma}$) was $3.2{\times}10^{-11}$ mol/L.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1801-1808
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• 2006

The interaction between whey carrier protein $\beta$-lactoglobulin type A and B (BLG-A and -B) and 2,2'-bipyridin n-hexyl dithiocarbamato Pd(II) nitrate (BPHDC-Pd(II)), a new heavy metal complex designed for anticancer property, was investigated by fluorescence spectroscopy combined with chemometry and circular dichroism (CD) techniques. A strong fluorescence quenching reaction of BPHDC-Pd(II) to BLG-A and -B was observed. Hence, BPHDC-Pd(II) complex can be bound to both BLG-A and -B, and quench the fluorescence spectra of the proteins. The quenching constant was determined using the modified Stern-Volmer equation. The binding parameters were evaluated by fluorescence quenching method. The results of binding study provided evidences presence of two and three sets of binding sites on the BLG-B and -A, respectively, for BPHDC-Pd(II) complex. Using fluorescence spectroscopy and chemometry, the ability of BLG-A and -B to form an intermediate upon interaction with BPHDC-Pd(II) complex was assessed. CD studies displayed that under influence of different concentrations of BPHDC-Pd(II) complex, the regular secondary structure of BLG-B had no significant changes, whereas for BLG-A a transition from $\alpha$-helix to $\beta$-structure was appeared. The results for both of BLG-A and -B displayed that BPHDC-Pd(II) complex can induce a conformational transition from the native form to an intermediate state with a slightly opened conformation, which is detectable with chemometry analyses.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.287-291
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• 1985

The addition of poly(styrenesulfonate) (PSS) to $Ru(bpy)_3^{2+}$ solutions shifted the emission peak by 3 nm to red, and increased emission intensity by 1.8 times. By contrast, poly(vinylsulfonate) (PVS) had little effect on the fluorescence spectrum. The effects of PSS on the spectral properties of $Ru(bpy)_3^{2+}$, were attributed to the presence of a hydrophobic phenyl group in PSS, which interact with $Ru(bpy)_3^{2+}$ by, at least in part, hydrophobic effect. The binding constant of $Ru(bpy)_3^{2+}$ to PSS in 0.1 M NaCl was $6{\times}10^4\;M^{-1}$, and this value was about $10^3$ times higher than those of methyl viologen ($MV^{2+}$) and $Cu^{2+}$. The Stern-Volmer constants of emission quenching of $Ru(bpy)_3^{2+}$ by $MV^{2+}$ and $Cu^{2+}$ in 0.1 M NaCl solutions were 426 and 40 $M^{-1}$, which correspond to second order rate constants($k_q$) of $1.1{\times}10^9\;and\; 1.0{\times}10^8\;M^{-1}s^{-1}$, respectively. The presence of PSS enhanced $K_{SV's}\;by\;{\sim}50$ times, whereas PVS increased the values only 1-4 times. The large enhancing effect of PSS, despite of lower charge density than PVS, was explained in terms of longer life-time of photoexcited $Ru(bpy)_3^{2+}$ bound to PSS and strong association of $Ru(bpy)_3^{2+}$ to PSS due to a specific interaction involving hydrophobic effect. The variation of $K_{SV's}$ on the concentrations of PVS and PSS were also investigated for $Ru(bpy)_3^{2+}-MV^{2+}\;and \;Ru(bpy)_3^{2+}-Cu^{2+}$ photoredox systems.

• The Korea Journal of Herbology
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• v.33 no.5
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• pp.105-110
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• 2018

Objectives : We tried to observe the fluorescence anisotropy and intensity of ethidium ion in the intercalating binding interaction between DNA and ethidium ions in the presence of berberine, and then tried to explain the effect of berberine on the intercalating interaction of ethidium ion with DNA. Methods : DNA(calf thymus DNA), berberine and ethidium bromide(EtBr) were purchased from Sigma-Aldrich Co. Proper amount of each compound was dissolved in 20 mM sodium phosphate buffer(pH 7.0) containing 100 mM of NaCl to prepare stock solutions. Collections of the fluorescence anisotropy and intensity data were performed on JASCO FP-8300 spectrofluorometer equipped with a polarizer and a Peltier temperature controller. The excitation of ethidium ion was done at 550 nm and the emission data were collected at 600 nm. For Stern-Volmer plot, the fluorescence data were collected at $18^{\circ}C$ and $30^{\circ}C$. Results : According to the results of this research, the weak competitive binding pattern between ethidium ion and berberine appeared in binding with DNA at low ratio of DNA to ethidium ion. But at high ratio of DNA to ethidium ion, this weak competition disappeared. Instead, berberine might bind to DNA by intercalating way. In other words, berberine could de-intercalate ethidium ion from DNA at low concentration of DNA relative to ethidium ion, but could not at high concentration of DNA relative to ethidium ion. In addition, the mechanism of fluorescence quenching of ethidium ion could also proceed differently, depending on the ratio of the amount of DNA to that of ethidium ion. Conclusions : The effect of berberine on the DNA-ethidium ion intercalating interaction could work differently, depending on the relative ratio of the amount of DNA to that of ethidium ion. This study also showed that fluorescence anisotropy analysis is very useful method to obtain detailed information for investigation of the complex binding interactions. In order to fully understand the mechanism of action of the pharmacological effect by berberine, studies on the effect of berberine on the action of proteins such as various enzymes closely related to berberine-induced medicinal effects should be continued.