Substitution effect of nitrogen atoms with carbon atoms in porphyrin on the electronic structure and excited states properties

Density functional theory (DFT) electronic structure calculations were carried out to predict the structures and the absorption and emission spectra for porphyrin and a series of carbaporphyrins-carbaporphyrin, adj-dicarbaporphyrin, opp-dicarbaporphyrin, tricarbaporphyrin and tetracarbaporphyrin. The ground- and excited-state geometries were optimized at the B3LYP/6-31g(d) and CIS/6-31g(d) level, respectively. The optimized ground-state geometry and absorption spectra of porphyrin, calculated by DFT and time-dependent DFT (TDDFT), are comparable with the available experimental values. Based on the optimized excited-state geometries obtained by CIS/6-31g(d) method, the emission properties are calculated using TDDFT method at the B3LYP/6-31g(d) level. The effects of the substitution of nitrogen atoms with carbon atoms at the center positions of porphyrin are discussed. The results indicate that the two-pyrrole nitrogens are important to the chemical and physical properties for porphyrin.

Synchronous fluorescence spectra of hemoglobin: A study of aggregation states in aqueous solutions

The synchronous fluorescence spectra of hemoglobin solutions are reported for the first rime. The main fluorescence peaks observed in the spectra are assigned. The effect of the concentration of hemoglobin solution on the spectra is studied. Characteristic fluorescence peaks due to the dimer and tetramer of hemoglobin molecules are recognized. (C) 1998 Academic Press.

STUDIES ON STATES OF CYTOCHROME-C MOLECULES IN AQUOUS SOLUTIONS USING SYNCHRONOUS FLUORESCENCE SPECTROSCOPY

The states of cytochrome C molecules in aquous solution were studied with synchronous fluorescence spectroscopy, It was found that the synchronous fluorescent spectra of cytochrome C were contributed by tyrosine and tryptophan residues separately at Delta lambda = 20 nm and Delta lambda = 80 nm, The peak position in synchronous fluorescent spectra of tyrosine residues in cytochrome C molecule does not change with its concentration, but that of tryptophan residue changes with its concentration, Only one peak at 340.0 nm was observed in the dilute solution of cytochrome C, With increasing the concentration of cytochrome C, a new peak at 304. 0 nm appeared. The peak at 340.0 nm disappeared and only one peak at 304.0 nm was observed at a higher concentration of cytochrome C, It may originate from the change of aggregation states of cytochrome C molecules and it was considered that the peak at 340.0 nm was attributed to the monomer and peak at 304.0 nm was due to the dimmer or oligomers. When urea was added into cytochrome C solution in which both monomer and dimmer or oligomers exist, cytochrome C molecules do not denature in the range of the specific concentrations of urea. The concentration of monomer of cytochrome C molecules increased and that of aggregation slates decreased by adding urea, Therefore, the synchronous fluorescence spectroscopy can be used to identify monomer and aggregation states of cytochrome C molecules.

FACTOR-ANALYSIS SPECTROPHOTOMETRY FOR THE SIMULTANEOUS DETERMINATION OF VALENCE STATES OF METALS

Two M(n+)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol systems for the simultaneous determination of the valence states of Cr and Fe using factor analysis were studied. (1) At pH 4.0, Cr(III) and Cr(VI) react with the reagent to form stable complexes and a slight difference in the wavelengths of maximum absorption (lambda(max.)) between the two complexes is observed when the sodium lauryl sulfate, which also acts as a solubilizing and sensitizing agent, is added, viz., 590 nm for Cr(III) and 593 nm for Cr(VI) complexes. (2) In the presence of ethanol, both Fe(II) and Fe(III) form 1:2 complexes with the reagent at pH 2.5-3.5 and the lambda(max.) of the Fe(II) and Fe(III) complexes is at 557 and 592 nm, respectively. In the target transformation factor analysis, the K coefficients calculated from the standard mixtures by classical least-squares analysis and a non-zero intercept added to each wavelength are used as the target vector instead of the pure component standards; this can decrease the analysis errors introduced by the interaction between the two species and by deviations from Beer's law.

Estimation of suspended sediment concentrations using Pulse-coherent Acoustic Doppler Profiler (PCADP)

The objective of the study is to investigate the suitability of using Pulse-coherent Acoustic Doppler Profiler (PCADP) to estimate suspended sediment concentration (SSC). The acoustic backscatter intensity was corrected for spreading and absorption loss, then calibrated with OBS and finally converted to SSC. The results show that there is a good correlation between SSC and backscatter intensity with R value of 0.74. The mean relative error is 22.4%. Then the time span of little particle size variation was also analyzed to exclude the influence of size variation. The correlation coefficient increased to 0.81 and the error decreased to 18.9%. Our results suggest that the PCADP can meet the requirement of other professional instruments to estimate SSC with the errors between 20% and 50%, and can satisfy the need of dynamics study of suspended particles.

Dynamics of the cold-water event off the southeast coast of the United States in the summer of 2003

The cold-water event along the southeast coast of the United States in the summer of 2003 is studied using satellite data combined with in situ observations. The analysis suggests that the cooling is produced by wind-driven coastal upwelling, which breaks the thermocline barrier in the summer of 2003. The strong and persistent southwesterly winds in the summer of 2003 play an important role of lifting the bottom isotherms up to the surface and away from the coast, generating persistent surface cooling in July-August 2003. Once the thermocline barrier is broken, the stratification in the nearshore region is weakened substantially, allowing further coastal cooling of large magnitudes by episodic southerly wind bursts or passage of coastally trapped waves at periods of a few days. These short-period winds or waves would otherwise have no effects on the surface temperature because of the strong thermocline barrier in summer if not for the low-frequency cooling produced by the persistent southwesterly winds.

Behavioural responses by yaks in different physiological states (lactating, dry or replacement heifers), when grazing natural pasture in the spring (dry and germinating) season on the Qinghai-Tibetan plateau

Using heterogeneous vegetation in alpine grassland through grazing is a necessary component of deintensification of livestock systems and conservation of natural environments. However, better understanding of the dynamics of animal feeding behaviour would improve pasture and livestock grazing managements, particularly in the early part of the spring season when forage is scarce. The changes in behaviour may improve the use of poor pastures. Then, enhancing management practices may conserve pasture and improve animal productivity. Grazing behaviour over 24 In periods by yaks in different physiological states (lactating, dry and replacement heifers) was recorded in the early, dry and later, germinating period of the spring season. Under conditions of inadequate forage, the physiological state of yaks was not the primary factor affecting their grazing and ruminating behaviour. Forage and sward state affected yaks' grazing and ruminating behaviour to a greater extent. Generally, yaks had higher intake and spent more time grazing and ruminating during the later part of the spring season, following germination of forage, than during the earlier dry part of the season. However, the live weight of yaks was less during pasture germination than during the early dry part of the season because the herbage mass is low, and the yaks have to expend much energy to seek feed at this particular time. (c) 2007 Elsevier B.V. All rights reserved.