Binding of Stimuli-Responsive Ruthenium Aqua Complexes with 9-Ethylguanine.

Stimuli-responsive ruthenium complexes proximal- and distal-[Ru(C10tpy)(C10pyqu) OH2]2+ (proximal-1 and distal-1; C10tpy = 4'-decyloxy-2,2':6',2″-terpyridine and C10pyqu = 2-[2'-(6'-decyloxy)-pyridyl]quinoline) were experimentally studied for adduct formation with a model DNA base. At 303 K, proximal-1 exhibited 1:1 adduct formation with 9-ethylguanine (9-EtG) to yield proximal-[Ru(C10tpy)(C10pyqu)(9-EtG)]2+ (proximal-RuEtG). Rotation of the guanine ligand on the ruthenium center was sterically hindered by the presence of an adjacent quinoline moiety at 303 K. Results from 1H NMR measurements indicated that photoirradiation of a proximal-RuEtG solution caused photoisomerization to distal-RuEtG, whereas heating of proximal-RuEtG caused ligand substitution to proximal-1. The distal isomer of the aqua complex, distal-1, was observed to slowly revert to proximal-1 at 303 K. In the presence of 9-EtG, distal-1 underwent thermal back-isomerization to proximal-1 and adduct formation to distal-RuEtG. Kinetic analysis of 1H NMR measurements showed that adduct formation between proximal-1 and 9-EtG was 8-fold faster than that between distal-1 and 9-EtG. This difference may be attributed to intramolecular hydrogen bonding and steric repulsion between the aqua ligand and the pendant moiety of the bidentate ligand..

Deep-sea in situ determination of sulfide using a sensitized chemiluminescent terbium complex.

A new chemiluminescence (CL) method based on the chemiluminescent reaction between sulfide and an acidic permanganate solution was used to quantify sulfide in seawater. A terbium-pipemidic acid complex was used as CL enhancer. The method was used to determine sulfide in the concentration range of 1-30 µmol/L in artificial seawater samples. The limit of detection of the method was 21 nmol/L sulfide. The sensitivity of the CL method was eight times higher than that of the CL method reported previously. Br- ions, which are conservative ions, interfered with sulfide. We investigated the effects of salinity, water temperature, and interfering chemicals,such asheavy-metal ions and organic matter, on the performance of the CL method. In addition, sulfite-spiked natural seawater samples were analyzed. The results demonstrate that the CL method can be used to develop a deep-sea sulfide analyzer.

A visible-light and temperature responsive host-guest system: the photoisomerization and inclusion complex formation of a ruthenium complex with cyclodextrins.

In the present study, we investigated the visible-light- and thermal-stimuli-responsive properties of a host-guest system based on proximal- and distal-[Ru(C10tpy)(C10pyqu)OH2]2+ complexes (proximal and distal-1; C10tpy = 4'-decyloxy-2,2':6',2''-terpyridine and C10pyqu = 2-[2'-(6'-decyloxy)-pyridyl]quinoline). The analogs of such ruthenium aqua complexes are well-known as metallodrugs and catalysts. The proximal isomer has a dicationic ruthenium center and hydrophobic alkyl chains on both ligands, with the two alkyl chains located close together. According to titration experiments, proximal-1 binds to γ-cyclodextrin (γ-CD) in aqueous media with a binding constant of K1:1 = 520 ± 60 M-1, which is much higher than the corresponding values for α-CD and ß-CD. Additional experiments indicated that the two alkyl chains were incorporated into the cavity of γ-CD. The photoisomerized complex, distal-1, exhibits thermal isomerization back to proximal-1 in the dark with a kobs = 7.26 ± 0.01 × 10-6 s-1. In the presence of γ-CD, the corresponding rate constant is 1.3 times higher, which is attributed to the steric repulsion of cyclodextrin and the aqua ligand by the inclusion complex formation between distal-1 and the cyclodextrins. The distal isomer has a lower affinity for CDs because the two alkyl chains are more separated. The repeated application of external stimuli to a mixture of proximal-1 and γ-CD resulted in a reproducible and reversible host-guest complex formation.

Proton spin relaxation study with pulsed NMR on the plasticization of Na+ ion-selective electrode membranes prepared from PVCs with different degrees of polymerization.

The proton spin-spin relaxation times (T2) of ion-selective electrode membranes with differences in the polymerization degree of the incorporated poly(vinyl chloride) (PVC) polymers were investigated. T2 measurements were performed using Hahn-Echo, Solid-Echo and Carr-Purcell-Meiboom-Gill (CPMG) pulse sequences. Analyses of the T2 measurements by Hahn-Echo pulse sequences could realize the estimation of the homogeneity and compatibility for a series of ion-selective electrode membranes and reveal a relationship with the electromotive force (EMF) response in the low-concentration region of the Na+ ions. On the other hand, the normalized derivative spectra from T2 measurements by Solid-Echo and CPMG pulse sequences could approximately visualize the degree of plasticization for such potentiometric polymeric membranes. Moreover, differences in the polymerization degrees of the incorporated PVCs were scarcely found to affect the selectivity coefficients of the Na+-ISEs based on bis(12-crown-4).

Bis(1-pyrenylmethyl)-2-benzyl-2-methyl-malonate as a Cu2+ Ion-Selective Fluoroionophore.

A new malonate possessing two pyrene moieties was synthesized as a fluoroionophore, and its structure and fluorescence spectroscopic properties were investigated. When excited at 344 nm in acetonitrile/chloroform (9:1, v/v), the synthesized bispyrenyl malonate has the fluorescence of intramolecular excimer (λem = 467 nm) emissions and not a pyrene monomer emission (λem = 394 nm). A large absolute fluorescence quantum yield was obtained in the solid state (ΦPL = 0.65) rather than in solution (ΦPL = 0.13). X-ray crystallography analysis clarified the molecular structure and alignment of the bispyrenyl malonate in the crystal phase, elucidating its fluorescence spectroscopic properties. Such analysis also suggests there are intramolecular C-H···π interactions and intermolecular π···π interactions between the pyrenyl rings. Interestingly, the synthesized bispyrenyl malonate exhibits excellent fluorescence sensing for the Cu2+ ion. Remarkable fluorescence intensity enhancement was only observed with the addition of the Cu2+ ion.

Enhanced chemiluminescence for trazodone trace analysis based on acidic permanganate oxidation in concurrent presence of rhodamine 6G.

A new sensitized chemiluminescence method by acidic permanganate oxidation was developed for the sensitive determination of trazodone. A fluorescent dye as used rhodamine 6G to increase a chemiluminescence intensity. Under optimum conditions, the liner range of the calibration curve was obtained for 1-5000 nmol/L. The limit of detection was calculated from 3σ of a blank was 0.23 nmol/L. The coexistent ions and substances had no interference with the chemiluminescence measurement. The chemiluminescence spectra were measured to elucidate a possible mechanism for the system. The present method was satisfactorily used in the determination of the drugs in pharmaceutical samples and animal serums.

Gas-particle concentrations of atmospheric polycyclic aromatic hydrocarbons at an urban and a residential site in Osaka, Japan: effect of the formation of atmospherically stable layer on their temporal change.

A comparative study on atmospheric polycyclic aromatic hydrocarbons (PAHs) in particulate matter and the gaseous phase was performed at an urban and a residential site in Osaka, Japan, during 2005-2006. PAH concentrations at the urban site were found to be approximately twice higher than those at the residential site. At both sites, particulate PAH concentrations increased mainly in winter while the trends of temporal change in gaseous PAH concentrations were not clearly observed. The main sources of PAHs were estimated to be local traffic, e.g., diesel engines with catalytic converter. PAH concentrations did not significantly negatively correlate with ozone concentrations and meteorological parameters. Gas-particle partitioning coefficients of representative PAHs with low molecular weight (LMW) significantly negatively correlated with ambient temperature, showing that temporal change in the LMW PAH concentrations in PM could be attributable to the shift of their gas-particle distribution caused by the change in ambient temperature. For the first time, we studied the effect of the formation of atmospherically stable layer following an increase in PAH concentrations in Japan. At the urban site, PAHs showed a significant positive correlation with potential temperature gradients, indicating that temporal variability in PAH concentrations would be dominantly controlled by the formation of atmospherically stable layer in Osaka area.

Determination of sulfide with acidic permanganate chemiluminescence for development of deep-sea in-situ analyzers.

A new chemiluminescence method is proposed for the determination of sulfide in seawater based on the chemiluminescence reaction between sulfide and an acidic permanganate solution. 3-Cyclohexylaminopropanesulfonic acid was used as a chemiluminescence enhancer. By use of this method, 1-150 µM of sulfide could be determined in artificial seawater. The limit of detection was 0.17 µM sulfide. We investigated the effects of salinity, water temperature, and interfering chemicals such as heavy-metal ions and organic matter. In addition, natural seawater spiked with sulfide was analyzed. The results showed that the CL method could be applied to a deep-sea sulfide analyzer.

Seasonal change in the atmospheric concentration of particulate polycyclic aromatic hydrocarbons in Ho Chi Minh City, Vietnam.

We analyzed atmospheric particulate polycyclic aromatic hydrocarbons (PAHs) in Ho Chi Minh City, Vietnam, for 19 months. The average concentrations of total PAHs at dry and rainy seasons were 4.28 +/- 2.83 and 15.71 +/- 8.21 ng m(-3), respectively. The use of motorcycles without catalytic converters, estimated to be main emission sources of PAHs, would be higher during the dry season. PAH concentrations show a negative correlation with sunshine duration (r = -0.51). Furthermore, the ratio of average PAH concentration in the dry season to that in the rainy season shows a positive correlation with photolytic half-life (r = 0.94). Thus, seasonal changes in PAH concentrations are attributable to their photolytic degradation.

Potentiometric performance of silver ion-selective electrodes based on tridentate Schiff base derivatives.

To examine the directivity for improving the silver ion discrimination ability of a Schiff base, three kinds of tridentate ligands were synthesized and compared with the similar quadridentate ligand as the silver ionophore. Among the Schiff base derivatives tested, 3-(2-pyridylethylimino)-2-butanoneoxime, having one oxime and a pyridine substituent, was found to be the best ionophore for a silver-ion electrode. The electrode based on this derivative exhibited good silver-ion selectivity, -log Kpot(Ag+,K+) = 3.8, comparable to that of a quadridentate Schiff base, N,N'-bis(2'-hydroxyimino-1'-phenylpropyleden)-1,3-propanediamine, reported previously, except for a pseudo Nernstian response (35.6 mV decade(-1)) with a wide silver-ion activity change in the activity change from 5.0 x 10(-7) to 7.9 x 10(-2) mol dm(-3).