Nature of the ring-closure process along the rearrangement of octa-1,3,5,7-tetraene to cycloocta-1,3,5-triene from the perspective of the electron localization function and catastrophe theory.

We analyze the behavior of the energy profile of the ring-closure process for the transformation of (3Z,5Z)-octa-1,3,5,7-tetraene 5 to (1Z,3Z,5Z)-cycloocta-1,3,5-triene 6 through a combination of electron localization function (ELF) and catastrophe theory (CT). From this analysis, concepts such as bond breaking/forming processes, formation/annihilation of lone pairs, and other electron pair rearrangements arise naturally through the reaction progress simply in terms of the different ways of pairing up the electrons. A relationship between the topology and the nature of the bond breaking/forming processes along this rearrangement is reported. The different domains of structural stability of the ELF occurring along the intrinsic reaction path have been identified. The reaction mechanism consists of six steps separated by fold and cusp catastrophes. The transition structure is observed in the third step, d(C1-C8) = 2.342 Å, where all bonds have topological signature of single bonds (C-C). The "new" C1-C8 single bond is not formed in transition state and respective catastrophe of the ELF field (cusp) is localized in the last step, d(C1-C8) ≈ 1.97 Å, where the two monosynaptic nonbonding basins V(C1) and V(C8) are joined into single disynaptic bonding basin V(C1,C8). The V(C1,C8) basin corresponds to classical picture of the C1-C8 bond in the Lewis formula. In cycloocta-1,3,5-triene 6 the single C1-C8 bond is characterized by relatively small basin population 1.72e, which is much smaller than other single bonds with 2.03 and 2.26e.

Photophysical properties of dipeptides containing substituted 3-(quinoxalin-6-yl) alanine. Spectroscopic studies and theoretical calculations.

The photophysical properties of excited states of two hybrid dipeptides [N-(3-(2,3-diphenylquinoxaline-6-ylo)alanylo) glycine], Pe-DPhQ, and [N-(3-(2,3 (pirydine-2-ylo) quinoxaline-6-ylo)alanylo) glycine], Pe-DPiQ, have been investigated by a combined solution-state study (absorption, emission) and quantum-mechanical (ab initio, DFT) calculations. The RHF and DFT B3LYP/6-31G (d,p) computations of the ground-state isomers of Pe-DPiQ dipeptide (open, half-closed, and closed) indicate that the most stable is the "open"-type structure with approximately equal (-44.43 degrees , -43.05 degrees ) dihedral angles describing rotation of the aromatic side rings with respect to the quinoxaline framework. This agrees with the literature findings that synthetic peptides are mostly unfolded. The experiments show that emission of Pe-DPiQ dipeptide is strongly temperature dependent, and at ambient and elevated temperatures the fluorescence is prevailing while the phosphorescence dominated emission spectra are observed at 77 K. On the basis of the decay curves that in the broad temperature range (rt-77 K) are biexponential (2 and 9 ns), it was concluded that at least its two major excited-state conformations may interconvert on the nanosecond time scale. The third component, of a small amplitude (10%) and a long time constant (25 ns), appears only in a new fluorescence band (570 nm) that grows up with the temperature increase. Analysis of the CIS/6-31G(d,p) results of the excited-state isomers of Pe-DPiQ supports the interpretation of experimental emission spectra and enables one to assign two excited-state conformations, demonstrating a tendency to keep one of their two side rings coplanar relative to the central quinoxaline plane, as Pe-DPiQ-I* (41.9 degrees , 6.3 degrees ) and Pe-DPiQ-II* (40.1 degrees , 4.5 degrees ) isomers contributing to the room temperature (403 nm) and 363 K (570 nm) fluorescence bands, respectively. The calculations also explain the electronic character of the corresponding S(1)<-->S(0) transitions and show that the state ordering of Pe-DPiQ resembles that of other diazines where the first singlet is of the npi* character while the S(2) and T(1) are the pipi* states. The reason for a strong phosphorescence is assigned to an effective spin-orbit coupling of appropriate singlet and triplet states that leads to ISC transitions and in result to population of the T(1) state and a phosphorescence from the T(1) state. From the present study, it was concluded that incorporation of quinoxaline moiety into the model peptides does not change the useful spectroscopic properties of the fluorophore and allows one to design its new analogues with improved activity and specificity.

Culturing of glial and neuronal cells on polysialic acid.

Although peripheral nerves exhibit regeneration capacities after transection injuries, the success of nerve repair depends crucially on the length of the gap. In addition to autologous nerve grafting as the conventional neurosurgical treatment to overcome long gaps, alternative strategies are needed. Numerous experimental studies have been undertaken to find the optimal material for production of artificial prostheses, which can be introduced as conduits between the nerve stumps. The current study follows the aim to establish polysialic acid (polySia), a homopolymer of alpha2,8-linked sialic acid residues, as a novel, biocompatible, and bioresorbable material for nerve tissue engineering. As a first step towards this goal, protocols for efficient coating of cell culture dishes with soluble polySia were established. In addition, primary nerve cells which are candidates for reconstructive therapies, including neonatal and adult Schwann cells, neural progenitor cells, spinal ganglionic neurons and motoneurons were cultured on polySia substrates. Cultures were evaluated with regard to cell survival and cell proliferation capacities. polySia turned out to be stable under cell culture conditions, and induced degradable and degradation products had no negative effects on cell cultures. Furthermore, polySia revealed its compatibility for several cell types derived from rat embryonic, postnatal and adult nervous tissue when used as a substrate.