Solvated cobalt(II) ions in neat 1,3-propanediamine (tn) and n-propylamine (pa) have been characterized by electronic absorption spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The equilibrium between tetrahedral and octahedral geometry for cobalt(II) ion has been observed in a neat pa solution, but not in neat diamine solutions such as tn and ethylenediamine (en). The thermodynamic parameters and equilibrium constant at 298 K for the geometrical equilibrium in pa were determined to be DeltaH degrees = -36.1 +/- 2.3 kJ mol(-1), DeltaS degrees = -163 +/- 8 J mol(-1) K(-1), and K(298) = 6.0 x 10(-3) M(-2), where K = [Co(pa)(6)(2+)]/{[Co(pa)(4)(2+)][pa](2)}. The equilibrium is caused by the large entropy gain in formation of the tetrahedral cobalt(II) species. The solvent exchange of cobalt(II) ion with octahedral geometry in tn and pa solutions has been studied by the (14)N NMR line-broadening method. The activation parameters and rate constants at 298 K for the solvent exchange reactions are as follows: DeltaH() = 49.3 +/- 0.9 kJ mol(-1), DeltaS() = 25 +/- 3 J mol(-1) K(-1), DeltaV() = 6.6 +/- 0.3 cm(3) mol(-1) at 302.1 K, and k(298) = 2.9 x 10(5) s(-1) for the tn exchange, and DeltaH() = 36.2 +/- 1.2 kJ mol(-1), DeltaS() = 35 +/- 6 J mol(-1) K(-1), and k(298) = 2.0 x 10(8) s(-1) for the pa exchange. By comparison of the activation parameters with those for the en exchange of cobalt(II) ion, it has been confirmed that the kinetic chelate strain effect is attributed to the large activation enthalpy for the bidentate chelate opening and that the enthalpic effect is smaller in the case of the six-membered tn chelate compared with the five-membered en chelate.

The present study investigates the effect on thympanic temperature of exposure to different light intensities for several hours during the daytime. Nine healthy young adult volunteers (two male, seven female) were exposed to bright light of 4000 lx or dim light of 100 lx during the daytime from 0930 to 1800 hours; the light condition was then kept at 100 lx for a further hour. Tympanic temperature was measured continuously at a neutral condition (28 degrees C, 60% relative humidity) from 1000 to 1800 hours. Urinary samples were collected from 1100 to 1900 hours every 2 h, and melatonin excretion rate was measured by enzyme immunoassay. Of nine subjects, six showed clearly lower tympanic temperatures in the bright compared with the dim condition from 1400 to 1800 hours. Average tympanic temperatures were significantly lower in the bright than in the dim condition from 1645 to 1800 hours. Melatonin excretion rate tended to be higher in the bright than in the dim condition. It was concluded that exposure to bright light of 4000 lx during the daytime for several hours could reduce tympanic temperature, compared with that measured in dim light of 100 lx.

The aim of the present study was to investigate the effect of exposure to differing light intensities for several hours during the daytime on the cutaneous vasodilatation and local forearm sweat rate induced by exercise. Seven healthy female subjects were exposed to bright light of 6000 lux (bright) or dim light of 100 lux (dim) during the daytime between 0900 hours to 1330 hours, followed by exposure to 150 lux until the test was over at 1600 hours. They spent their time in neutral conditions (29 degrees C, 40% relative humidity) from 0900 hours to 1500 hours, and then exercised on a cycle ergometer for 30 min at 50% maximal physical work capacity. Average tympanic temperatures were significantly lower in bright than in dim from 1133 hours to 1430 hours. The onset of cutaneous vasodilatation and local forearm sweating occurred at significantly lower tympanic temperature (Tty) during exercise after bright than after dim. After exercise, the cessation of forearm sweating and the rapid change of skin blood flow occurred at significantly lower Tty after bright than after dim. It was concluded that exposure to bright light over several hours during the daytime could reduce Tty and shift the threshold Tty for cutaneous vasodilatation and forearm sweating to a lower level.

The subjects were exposed to bright or dim light during the daytime. Compared to dim light exposure, bright light exposure induced a steeper slope in the regression line between the skin blood flow of the forearm and mean body temperature under an external heat load in the evening.

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