Application of MCD spectroscopy and TD-DFT to a highly non-planar porphyrinoid ring system. New insights on red-shifted porphyrinoid spectral bands

The first magnetic circular dichroism (MCD) spectra are reported for tetraphenyltetraacenaphthoporphyrin (TPTANP). The impact on the electronic structure of steric interactions between the fused acenaphthalene rings and the meso-tetraphenyl substituents is explored based on an analysis of the optical spectra of the Zn(II) complex (ZnTPTANP) and the free base dication species ([H4TPTANP]2+). In the case of ZnTPTANP, significant folding of the porphyrinoid ligand induces a highly unusual MCD-sign reversal providing the first direct spectroscopic evidence of ligand nonplanarity. Density functional theory (DFT) geometry optimizations for a wide range of Zn(II) porphyrinoids based on the B3LYP functional and TD-DFT calculations of the associated UV-visible absorption spectra are reported, allowing a complete assessment of the MCD data. TPTANP complexes are found to fall into a class of cyclic polyenes, termed as soft MCD chromophores by Michl (J. Pure Appl. Chem. 1980, 52, 1549.), since the signs of the Faraday A1 terms observed in the MCD spectrum are highly sensitive to slight structural changes. The origin of an unusually large red shift of the main B (or Soret) band of MTPTANP (the most red shifted ever reported for fused-ring-expanded metal porphines) and of similar red shifts observed in the spectra of other peripherally crowded porphyrinoid complexes is also explored and explained on this basis.     

Sulfur K-Edge EXAFS Studies of Cadmium-, Zinc-, Copper-, and Silver-Rabbit Liver Metallothioneins

The structures of metal-thiolate clusters in Zn(7)-MT, Cd(7)-MT, Cu(12)-MT, Ag(12)-MT, and Ag(17)-MT from rabbit liver have been investigated by sulfur K-edge X-ray absorption spectroscopy (XAS). In addition to providing metal-cysteinyl sulfur bond lengths, the sulfur K-edge EXAFS data provide the first direct evidence for mixtures of bridging and terminal sulfurs in Cu-MT and Ag-MT. The Zn-S and Cd-S bond lengths for tetrahedrally coordinated Zn(4)(SPh)(10)(2-) and Cd(4)(SPh)(10)(2-) compounds obtained from sulfur K-edge EXAFS data are 2.35 +/- 0.03 and 2.52 +/- 0.02 ?, respectively. Zn-S and Cd-S bond distances of 2.34 +/- 0.03 ? for Zn(7)-MT and 2.54 +/- 0.02 ? for Cd(7)-MT, respectively, calculated from sulfur K-edge EXAFS measurements, are consistent with the previously reported results from metal K-edge EXAFS data. Analysis of the sulfur K-edge EXAFS data for Cu(12)-MT indicates that Cu(I) is trigonally coordinated to sulfurs at a distance of 2.25 +/- 0.01 ?. Significant changes in CD spectra observed between Ag(12)-MT 1 and Ag(17)-MT 1 indicate that the modification of the three-dimensional structure occurs when Ag(17)-MT 1 is formed from Ag(12)-MT 1 as Ag(I) is added to the Ag(12)-MT 1. The Ag-S bond distances of 2.45 +/- 0.02 and 2.44 +/- 0.03 ? in Ag(1)(2)-MT 1 and Ag(1)(7)-MT 1, respectively, calculated from the sulfur K-edge EXAFS measurements, lead us to conclude that the Ag(I) in both Ag(1)(2)-MT 1 and Ag(1)(7)-MT 1 is digonally coordinated by thiolates. The number of metals bonded to sulfur in both model compounds and metal-containing metallothioneins is estimated from sulfur K-edge EXAFS measurements to be in the range 1.2-1.7, depending on the fraction of bridging sulfurs present in compounds. Unlike the spectral data recorded during Cu(I) binding, where sharp changes take place past 12 Cu(I), the CD data for Ag-MT 1 show little variation over the entire range of Ag(I):MT molar ratios. This result, established by both low- and high-energy optical methods, suggests that the three-dimensional structure of the metal-binding sites in metallothioneins is strongly influenced by the fraction of bridging sulfur. This analysis is the first to provide direct support for the presence of a clustered Ag-S structure for the Ag(17)-MT 1 species. These data also suggest that the structures in Ag(I) and Cu(I) metallothioneins are probably quite different.     

Developing the roots of modelling conceptions: ‘mathematical modelling is the life of the world’

A study conducted with 25 Year 6 primary school students investigated the potential for a short classroom intervention to begin the development of a Modelling conception of mathematics on the way to developing a sense of mathematics as a way of thinking about life. The study documents the developmental roots of the cognitive activity, actions and conceptions of both modelling and mathematics that these beginners to modelling displayed. Understanding the conceptions of mathematics that students might hold or be developing and how these can be influenced in early schooling are essential ingredients in any plans for introducing modelling seriously into primary school classrooms. The majority of the students (22/25) were identified as displaying a developing conception of modelling as a way of problem handling. The three other students displayed the developmental roots of a way of understanding the world conception of modelling. These three students also displayed a Modelling conception of mathematics with one showing indications of developing towards a Life conception of mathematics.     

Pentacene‐Fused Diporphyrins

In this work, we report the synthesis, spectroscopic characterization, and theoretical analysis of a linearly conjugated pentacene‐fused porphyrin dimer and cross‐conjugated quinone‐fused dinaphtho[2,3]porphyrins. These multichromophoric systems display non‐typical UV‐visible absorptions of either porphyrins or pentacenes/quinones. UV‐visible, emission and magnetic circular dichroism (MCD) spectroscopy suggest strong electronic interactions among the multichromophores in the system. DFT calculations revealed the delocalization of the HOMOs and LUMOs spanning the entire dimer and linker assembly. The pentacene‐fused porphyrin dimer is significantly more stable than both the corresponding pentacene and the heptacene derivatives. The availability of these huge π‐extended and electronically highly interactive multichromophoric systems promises unprecedented electronic and photophysical properties.     

Implementation of IBL in Europe from an Australasian perspective

In this paper the situation in Australasia with respect to research, curricula and practice in inquiry-based learning in mathematics education is examined. As an organising frame the work of researchers in the Mathematics Education Research Group of Australasia (MERGA) was examined for points of intersection with several of the papers that have arisen from the international PRIMAS project, one of several projects funded by the European Union which follow the recommendations of the Rocard Report (Rocard et al. 2007). Although MERGA services researchers in countries such as Singapore in addition to Australia and New Zealand, a survey of outputs of members showed that the latter two countries had more of a tradition of inquiry-based learning practices and research in mathematics education than did Asian countries under the MERGA umbrella such as Singapore. For this reason the focus here is on mathematics education in the schools in these two countries and the classroom research in them that extends or complements the research or issues raised in other papers in this issue of ZDM.