Giant porphyrin disks: control of their self-assembly at liquid-solid interfaces through metal-ligand interactions

The synthesis and self-assembly behaviour of porphyrin dodecamers 1H(2) and Zn-1, which consist of twelve porphyrins that are covalently attached to a central aromatic core, is described. According to STM, 1D and 2D NMR studies, and molecular modelling calculations, the porphyrin dodecamers have a yo-yo-shaped structure. Their large pi surface, in combination with their disk-like shape, allows them to form self-assembled structures, which in the case of Zn-1 can be tuned by adding bidentate ligands. The self-assembly of the molecules at the liquid-solid interface of 1-phenyloctane with highly oriented pyrolytic graphite or Au(111) was imaged by using STM. The porphyrin disks in the self-assembled arrays have an edge-on orientation on the surface. The addition of bidentate axial ligands to the Zn-1 molecules in the arrays allows their intermolecular distance to be precisely controlled.     

Tris-cyclometalated iridium(III) complexes of carbazole(fluorenyl)pyridine ligands: synthesis, redox and photophysical properties, and electrophosphorescent light-emitting diodes

Using ligands synthesized by Suzuki cross-coupling methodology, new phosphorescent homoleptic tris-cyclometalated complexes have been obtained, namely fac-[Ir(Cz-2-Fl(n)Py)(3)] (1 d-f) and fac-[Ir(Cz-3-Fl(n)Py)(3)] (2 d-f), which are solution-processible triplet emitters (Cz denotes N-hexylcarbazole, n is the number of 9,9'-dihexylfluorene (Fl) units (n=0,1,2) and Py is pyridine). In all cases, Py and Fl are substituted at the 2- and 2,7-positions, respectively, and Cz moieties are substituted by either Py or Fl at the 2- or 3-positions, in series 1 and 2, respectively. The oxidation potential of 1 d studied by cyclic voltammetry ({E{{{\rm ox}\hfill \atop 1/2\hfill}}}=0.14 V, versus Ag/AgNO(3), CH(2)Cl(2)) is less positive (i.e. raised HOMO level) compared to that of the isomer 2 d ({E{{{\rm ox}\hfill \atop 1/2\hfill}}}=0.30 V), where the Cz-nitrogen is meta to the Ir center. Ligand-centered oxidations occur at more positive potentials, leading to 7+ oxidation states with good chemical reversibility and electrochemical quasi-reversibility, for example, for 2 f {E{{{\rm ox}\hfill \atop {\rm pa}\hfill}}} =0.45 (1e), 0.95 (3e), 1.24 V (3e). Striking differences are seen in the solution-state photophysical data between complexes [Ir(Cz-2-Py)(3)] (1 d) and [Ir(Cz-3-Py)(3)] (2 d), in which the Cz moiety is bonded directly to the metal center: for the latter there is an 85 nm blue-shift in emission, a decrease in the luminescence lifetime and an increase in the PLQY value. Organic light emitting devices were made by spin-coating using polyspirobifluorene:bis(triphenyl)diamine (PSBF:TAD) copolymer as host and the complexes 1 d or 2 d as dopants. Turn-on voltages are low (3-4 V). With 1 d orange light is emitted at lambda(max)=590 nm with an EQE of 1.3 % (at 7.5 mA cm(-2)) and an emission intensity (luminance) of 4354 cd m(-2) (at 267 mA m(-2)). The green emission from 2 d devices (lambda(max)=500 nm) is due to the reduced electron-donating ability of the carbazole unit in 2 d. Recording the EL spectra of the 1 d device at 6 V (current density, 100 mA cm(-2)) established that the time to half brightness was about 9 h under continuous operation with no change in the spectral profile, confirming the high chemical stability of the complex.     

Examining the effect of the dipole moment on charge separation in donor-acceptor polymers for organic photovoltaic applications

A new low band gap copolymer PBB3 containing [6,6']bi[thieno[3,4-b]thiophenyl]-2,2'-dicarboxylic acid bis-(2-butyloctyl) ester (BTT) and 4,8-bis(2-butyloctyl)benzo[1,2-b:4,5-b']dithiophene (BDT) units was synthesized and tested for solar cell efficiency. PBB3 showed a broad absorbance in the near-IR region with a substantially red-shifted (by more than 100 nm) λ(max) at 790 nm as compared to the PTB series of polymers, which have been previously reported. The PBB3 polymer also showed both a favorable energy level match with PCBM (with a LUMO energy level of -3.29 eV) and a favorable film domain morphology as evidenced by TEM images. Despite these seemingly optimal parameters, a bulk heterojunction (BHJ) photovoltaic device fabricated from a blend of PBB3 and PC(71)BM showed an overall power conversion efficiency (PCE) of only 2.04% under AM 1.5G/100 mW cm(-2). The transient absorption spectra of PBB3 showed the absence of cationic and pseudo charge transfer states that were observed previously in the PTB series polymers, which were also composed of alternating thienothiophene (TT) and BDT units. We compared the spectral features and electronic density distribution of PBB3 with those of PTB2, PTB7, and PTBF2. While PTB2 and PTB7 have substantial charge transfer characteristics and also relatively large local internal dipoles through BDT to TT moieties, PTBF2 and PBB3 have minimized internal dipole moments due to the presence of two adjacent TT units (or two opposing fluorine atoms in PTBF2) with opposite orientations or internal dipoles. PBB3 showed a long-lived excitonic state and the slowest electron transfer dynamics of the series of polymers, as well as the fastest recombination rate of the charge-separated (CS) species, indicating that electrons and holes are more tightly bound in these species. Consequently, substantially lower degrees of charge separation were observed in both PBB3 and PTBF2. These results show that not only the energetics but also the internal dipole moment along the polymer chain may be critical in maintaining the pseudocharge transfer characteristics of these systems, which were shown to be partially responsible for the high PCE device made from the PTB series of low band gap copolymers.     

On-line (HPLC-NMR) and off-line phytochemical profiling of the Australian plant, Lasiopetalum macrophyllum

On-line (HPLC-NMR) and off-line (HPLC, NMR and MS) methodologies were used to profile the constituents present in the crude extract of Lasiopetalum macrophyllum. On-flow and stop-flow HPLC-NMR supported the presence of trans-tiliroside and permitted partial identification of cis-tiliroside and 4'-methoxy-trans-tiliroside. Off-line isolation led to the unequivocal identification of four flavanoid glycosides including a new structural derivative, 4'-methoxy-cis-tiliroside. This is the first report of flavonoid glycosides occurring in this plant genus. In addition, a number of structure revisions have been proposed for previously reported flavonoid glycosides that were incorrectly assigned.     

Photochemical [2 + 2] cycloaddition reactions of 6-alkenyl-3-phenylcyclohex-2-en-1-ones: using biradical conformation control to account for exceptions to the "rule of five"

A series of 6-alkenyl-3-phenylcyclohex-2-enones has been synthesised and the structures of the products obtained from them on irradiation have been determined. The 6-propenyl compounds afforded a tricyclic 'parallel' [2 + 2] cycloaddition product and a bicyclic enone resulting from hydrogen abstraction in the biradical intermediate. The 6-butenyl and 6-pentenyl analogues gave 'crossed' cycloaddition products only. Although the regiochemistry of these cycloaddition reactions cannot be explained in terms of the 'rule of five', it is compatible with the concept of 'biradical conformation control' which is based on a consideration of the energy and structure of the possible 1,4-biradical intermediates.     

Regular elements in generalized hermitian algebras

A generalized Hermitian (GH) algebra is a special Jordan algebra that is at the same time a spectral order-unit space. In this paper we characterize the von Neumann regular elements in a GH-algebra, relate maximal pairwise commuting subsets of the algebra to blocks in its projection lattice, and prove a Gelfand-Naimark type representation theorem for commutative GH-algebras.     

Finding low cost TSP and 2-matching solutions using certain half-integer subtour vertices

Consider the traveling salesman problem (TSP) defined on the complete graph, where the edge costs satisfy the triangle inequality. Let TOUR denote the optimal solution value for the TSP. Two well-known relaxations of the TSP are the subtour elimination problem and the 2-matching problem. If we let SUBT and 2M represent the optimal solution values for these two relaxations, then it has been conjectured that TOUR/SUBT ≤4/3, and that 2M/SUBT ≤10/9.In this paper, we exploit the structure of certain 1/2-integer solutions for the subtour elimination problem in order to obtain low cost TSP and 2-matching solutions. In particular, we show that for cost functions for which the optimal subtour elimination solution found falls into our classes, the above two conjectures are true. Our proofs are constructive and could be implemented in polynomial time, and thus, for such cost functions, provide a 4/3 (or better) approximation algorithm for the TSP.     

Age-Related Carbonylation of Fibrocartilage Structural Proteins Drives Tissue Degenerative Modification

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Tightness in subset bounds for coherent configurations

Association schemes have many applications to the study of designs, codes, and geometries and are well studied. Coherent configurations are a natural generalization of association schemes, however, analogous applications have yet to be fully explored. Recently, Hobart [Mich. Math. J. 58:231–239, 2009] generalized the linear programming bound for association schemes, showing that a subset Y of a coherent configuration determines positive semidefinite matrices, which can be used to constrain certain properties of the subset. The bounds are tight when one of these matrices is singular, and in this paper we show that this gives information on the relations between Y and any other subset. We apply this result to sets of nonincident points and lines in coherent configurations determined by projective planes (where the points of the subset correspond to a maximal arc) and partial geometries.     

The traveling salesman problem on cubic and subcubic graphs

We study the traveling salesman problem (TSP) on the metric completion of cubic and subcubic graphs, which is known to be NP-hard. The problem is of interest because of its relation to the famous 4/3-conjecture for metric TSP, which says that the integrality gap, i.e., the worst case ratio between the optimal value of a TSP instance and that of its linear programming relaxation (the subtour elimination relaxation), is 4/3. We present the first algorithm for cubic graphs with approximation ratio 4/3. The proof uses polyhedral techniques in a surprising way, which is of independent interest. In fact we prove constructively that for any cubic graph on $n$ vertices a tour of length $4n/3-2$ exists, which also implies the 4/3-conjecture, as an upper bound, for this class of graph-TSP. Recently, Mömke and Svensson presented an algorithm that gives a 1.461-approximation for graph-TSP on general graphs and as a side result a 4/3-approximation algorithm for this problem on subcubic graphs, also settling the 4/3-conjecture for this class of graph-TSP. The algorithm by Mömke and Svensson is initially randomized but the authors remark that derandomization is trivial. We will present a different way to derandomize their algorithm which leads to a faster running time. All of the latter also works for multigraphs.