Tuning of excited-state intramolecular proton transfer (ESIPT) fluorescence of imidazo[1,2-a]pyridine in rigid matrices by substitution effect.

2-(2'-Hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP, 1) and its derivatives are synthesized, and their fluorescence properties are studied. Although all the compounds show faint dual emission (Φ ≈ 0.01), which is assigned to the normal and excited-state intramolecular proton transfer (ESIPT) fluorescence in a fluid solution, they generally display efficient ESIPT fluorescence (Φ up to 0.6) in a polymer matrix. The introduction of electron-donating and electron-withdrawing groups into the phenyl ring causes blue and red shifts of the ESIPT fluorescence emission band, respectively. On the other hand, the introduction of such groups into the imidazopyridine part results in fluorescence shifts in the opposite directions. The results of ab initio quantum chemical calculations of the intramolecular proton-transferred (IPT) state are well in line with the ESIPT fluorescence energies. The plots of the calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels against the Hammett substituent constants (σ) show good linearity with different slopes, which can rationalize the effect of the substituent and its position on the IPT state. Therefore, we have developed a series of HPIPs as new ESIPT fluorescent compounds and demonstrate that ESIPT fluorescence properties would be rationally tuned using quantum chemical methods.

Diurnal rhythms in fetal heart rate baseline and sustained fetal tachycardia in twin pregnancy.

OBJECTIVE: To elucidate the synchronization of phases of diurnal rhythms in fetal heart rate (FHR) baseline between twin fetuses and the occurrence of sustained fetal tachycardia. METHODS: FHR was simultaneously recorded in twins for 24 h in 7 monochorionic diamniotic (MD) and 8 dichorionic diamniotic (DD) twin pregnancies at 35 to 38 weeks of gestation. The diurnal rhythms of the hourly mean FHR baseline were tested in each fetus, and the time of occurrence of sustained fetal tachycardia was compared between twins. The correlation coefficients and phase lags of diurnal rhythms between the hourly mean FHR baselines of twins were calculated in each case. RESULTS: There were significant diurnal rhythms in the hourly mean FHR baselines of all twin fetuses (p<0.01). The patterns of diurnal rhythms were similar for each pair of twins, with the exception of the periods of sustained fetal tachycardia. Sustained fetal tachycardia was not coincident between twins. Analysis in which the periods of sustained fetal tachycardia were excluded demonstrated a significant correlation between the hourly mean FHR baselines of twins in all cases (p<0.01). In the case of DD twins, the phase lag between twins was 0; however, phase lags were observed in 4 cases of MD twins. CONCLUSIONS: The results of this study revealed that the diurnal rhythms in the FHR baseline correlated well between twins, and that the occurrences of sustained fetal tachycardia were completely independent.

Colorless, transparent, dye-doped polymer films exhibiting tunable luminescence color: controlling the dual-color luminescence of 2-(2'-hydroxyphenyl)imidazo[1,2-a]pyridine derivatives with the surrounding matrix.

Colorless, transparent, polymer films including 2-(2'-hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP) derivatives, 1 and 2, are prepared by a spin-coating method. The observed emission spectra upon photoexcitation of these polymer films were composed of dual emission bands: the normal luminescence at 370-410 nm (purple) and the greatly Stokes-shifted emission at 520-580 nm (yellow) assigned as the excited-state intramolecular proton transfer (ESIPT) luminescence. Relative intensity of the two emissions varied according to the polymer matrices, resulting in change in the luminescent color of the dye-doped polymer films. Particularly, the luminescence properties of 6-cyano HPIP, 2, are highly susceptible to the surrounding environment, and therefore successfully tuned to produce a wide range of colors, from purple to orange, by changing its concentration within and the type of the polymer matrix. This observation can be ascribed to the formation of a relatively weak intramolecular hydrogen bond resulting from the electron-withdrawing 6-cyano group. Thus, we demonstrate large variations in emission color can be achieved using interactions of the single component with the surrounding matrix. These results offer promise as a convenient and effective method for a wide-range tuning the luminescence colors of dye-doped polymer films.

Fabrication of colorless organic materials exhibiting white luminescence using normal and excited-state intramolecular proton transfer processes.

Organic, white luminescent materials were fabricated using a mixture of proton-transfer and nonproton-transfer fluorophores. 2'-Methoxy and 2'-hydroxy derivatives of 2-phenylimidazo[1,2-a]pyridine (PIP) have similar UV-absorption properties; however, they exhibit mechanistically different luminescence respectively ascribable to the normal (∼420 nm) and excited-state intramolecular proton transfer processes (∼530 nm) in the solid state. UV-irradiation of mixed solids excites both components concurrently and results in efficient white luminescence composed of two independent emissions without involving energy transfer process. White luminescent solids are easily transformed into vapor-deposited films under mild conditions, and a colorless and transparent thin film by dissolving in PMMA.

Analysis of the influence of diurnal variation in maternal movements on fetal heart rate acceleration.

To determine the influence of diurnal variation in maternal movements (MM) on fetal heart rate (FHR) accelerations, 24-hour maternal heart rates (MHR), MM and FHR recordings were made simultaneously on nine healthy pregnant women at 36-39 weeks of gestation. Correlations between the diurnal variations in maternal factors and FHR parameters; that is, baseline FHR, amplitude, duration and hourly percentage of time spent in accelerations, were examined. Only a few cases showed a significant correlation between acceleration parameters and the diurnal variation of MHR or MM, while most cases indicated a high correlation between the diurnal variation in baseline FHR and that of maternal factors. In conclusion, the occurrence and form of accelerations might be independent of maternal activity.

Differences in fractal structure of adult heart rate fluctuation between successive rapid eye movement sleeps: case report.

The dynamics of fractal structures of heart rate (HR) fluctuations in successive rapid eye movement sleeps (REMS) was investigated in a healthy male. Fractal analysis using a purposely-devised method was carried out at 10-min time series of HR, which were being recorded simultaneously by an electroencephalogram at night. Scaling relationships showed three slopes (alpha(s)). The mean alphas below one cross-over point (< 6.0 s), mean alpha(m) between two cross-over points, and mean alpha1 above another cross-over point (> 12.0 s) during REMS changed from 2.0, 1.0, and 0.3 in the third cycle to 2.0, 0.9, and 1.2 in the fourth cycle. The present study demonstrates the differences in multiscaled fractal structures of HR fluctuations between the successive REMS in a particular case.