Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Synchronous fluorescence and UV–vis spectroscopic studies of interactions between the tetracycline antibiotic, aluminium ions and DNA with the aid of the Methylene Blue dye probe

Synchronous fluorescence spectroscopy (SFS) was applied for the investigation of interactions of the antibiotic, tetracycline (TC), with DNA in the presence of aluminium ions (Al3+). The study was facilitated by the use of the Methylene Blue (MB) dye probe, and the interpretation of the spectral data with the aid of the chemometrics method, parallel factor analysis (PARAFAC). Three-way synchronous fluorescence analysis extracted the important optimum constant wavelength differences, Δλ, and showed that for the TC–Al3+–DNA, TC–Al3+ and MB dye systems, the associated Δλ values were different (Δλ = 80, 75 and 30 nm, respectively). Subsequent PARAFAC analysis demonstrated the extraction of the equilibrium concentration profiles for the TC–Al3+, TC–Al3+–DNA and MB probe systems. This information is unobtainable by conventional means of data interpretation. The results indicated that the MB dye interacted with the TC–Al3+–DNA surface complex, presumably via a reaction intermediate, TC–Al3+–DNA–MB, leading to the displacement of the TC–Al3+ by the incoming MB dye probe.

Getting Excited About Software Programming

Invited one hour presentation at Microsoft Tech Ed 2009 about getting students interested in games programming at QUT.

Layered titanate nanofibers as efficient adsorbents for removal of toxic radioactive and heavy metal ions from water

Titanate nanofibers with two formulas, Na2Ti3O7 and Na1.5H0.5Ti3O7, respectively, exhibit ideal properties for removal of radioactive and heavy metal ions in wastewater, such as Sr2+ , Ba2+ (as substitute of 226Ra2+), and Pb2+ ions. These nanofibers can be fabricated readily by a reaction between titania and caustic soda and have structures in which TiO6 octahedra join each other to form layers with negative charges; the sodium cations exist within the interlayer regions and are exchangeable. They can selectively adsorb the bivalent radioactive ions and heavy metal ions from water through ion exchange process. More importantly, such sorption finally induces considerable deformation of the layer structure, resulting in permanent entrapment of the toxic bivalent cations in the fibers so that the toxic ions can be safely deposited. This study highlights that nanoparticles of inorganic ion exchangers with layered structure are potential materials for efficient removal of the toxic ions from contaminated water.

Corona ions from overhead transmission voltage powerlines : effect on DC e-field and ambient particle concentration levels

Along with their essential role in electricity transmission and distribution, some powerlines also generate large concentrations of corona ions. This study aimed at comprehensive investigation of corona ions, vertical dc e-field, ambient aerosol particle charge and particle number concentration levels in the proximity of some high/sub-transmission voltage powerlines. The influence of meteorology on the instantaneous value of these parameters, and the possible existence of links or associations between the parameters measured were also statistically investigated. The presence of positive and negative polarities of corona ions was associated with variation in the mean vertical dc e-field, ambient ion and particle charge concentration level. Though these variations increased with wind speed, their values also decreased with distance from the powerlines. Predominately positive polarities of ions were recorded up to a distance of 150 m (with the maximum values recorded 50 m downwind of the powerlines). At 200 m from the source, negative ions predominated. Particle number concentration levels however remained relatively constant (103 particle cm-3) irrespective of the sampling site and distance from the powerlines. Meteorological factors of temperature, humidity and wind direction showed no influence on the electrical parameters measured. The study also discovered that e-field measurements were not necessarily a true representation of the ground-level ambient ion/particle charge concentrations.

Ions in motor vehicle exhaust and their dispersion near busy roads

Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm-3) was about one-half of that near motorways (1211 cm-3) and about twice as high as that in the urban background (269 cm-3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density (R2=0.3 at p<0.05) and correlated well with each other in real time (R2=0.87 at p<0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120-150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2m to 5m of the kerb. Measured concentrations decreased to background at about 15m from the kerb when the wind speed was 1.3 m s-1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.

Sodium niobate adsorbents doped with tantalum (TaV) for the removal of bivalence radioactive ions in waste waters

Sodium niobates doped with different amount of tantalum (TaV) were prepared via thermal reaction process. It was found pure nanofibril and bar-like solids can be obtained when tantalum was introduced into the reaction system. For the well-crystallized fibril solids, the Na+ ions are difficult to be exchanged, and the radioactive ions such as Sr2+ and Ra2+ ions just deposit on the surface of the fibers during the sorption process, resulting in lower sorption capacity and distribution coefficients (Kd)`. However, the bar-like solids are poorly-crystallized and have lots of exchangeable Na+ ions. They are able to remove highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ ions. Even in the presence of lots of Na+ ions, they also have higher Kd. More importantly, such sorption finally intelligently triggers considerable collapse of the structure, resulting in the entrapment of the toxic bivalent cations permanently in the solids so that they can be safely disposed. This study highlights new opportunities for the preparation of Nb-based adsorbents to efficiently remove the toxic radioactive ions from contaminated water.