Photophysical properties of a C6 hydrocarbon linked porphyrin dimer

The synthesis and characterisation of a C₆ hydrocarbon linked porphyrin dimer and its zinc complex is described. From fluorescence quantum yields and excited singlet and triplet state lifetimes, recorded for the dimers and the corresponding monomer species, it is suggested that the dimeric porphyrins exist in solution in open and closed conformations. The open conformations retain photophysical properties similar to those of the relevant monomeric species but the closed conformations do not fluoresce.     

Oxygen deficiency in oxide films grown by PLD

The incorporation of oxygen atoms in oxide films grown by pulsed laser deposition depends upon the oxygen pressure and laser power density. By carefully controlling these two parameters it is possible to control the oxygen deficiency in the samples, and thus to change their physical properties from insulating and transparent to absorbing and conducting. By using X-ray diffraction, Rutherford backscattering spectroscopy and resistivity measurements, we show that depending upon the oxide materials oxygen deficiency in the films can induce either the growth of stable sub-oxide phases or the formation of nanocomposite films by phase separation. The first case corresponds to oxides with a mixed valency cation like Ti, which leads to the formation of stable, crystalline and highly conductive TiO_x sub-oxide phases. The second case is well described by the indium tin oxides (ITO) in which a large oxygen deficiency leads to metallic clusters embedded into a stoichiometric matrix, i.e. nanocomposite films. This phenomenon is due to the fact that sub-oxides of these compounds are not stable and thus the oxygen deficiency induced a phase separation.     

Theoretical analysis of aggregation in block‐copolymer films: The optical signature

We focus this work on the theoretical investigation of the block‐copolymer poly[oxyoctyleneoxy‐(2,6‐dimethoxy‐1,4phenylene‐1,2‐ethinylene‐phenanthrene‐2,4diyl) named as LaPPS19, recently proposed for optoelectronic applications. We used for that a variety of methods, from molecular mechanics to quantum semiempirical techniques (AM1, ZINDO/S‐CIS). Our results show that as expected isolated LaPPS19 chains present relevant electron localization over the phenanthrene group. We found, however, that LaPPS19 could assemble in a π‐stacked form, leading to impressive interchain interaction; the stacking induces electronic delocalization between neighbor chains and introduces new states below the phenanthrene‐related absorption; these results allowed us to associate the red‐shift of the absorption edge, seen in the experimental results, to spontaneous π‐stack aggregation of the chains. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Coexistence of self-organized criticality and intermittent turbulence in the solar corona

An extended data set of extreme ultraviolet images of the solar corona provided by the SOHO spacecraft is analyzed using statistical methods common to studies of self-organized criticality (SOC) and intermittent turbulence (IT). The data exhibit simultaneous hallmarks of both regimes: namely, power-law avalanche statistics as well as multiscaling of structure functions for spatial activity. This implies that both SOC and IT may be manifestations of a single complex dynamical process entangling avalanches of magnetic energy dissipation with turbulent particle flows.     

Cyto-mechanoresponsive polyelectrolyte multilayer films

Cell adhesion processes take place through mechanotransduction mechanisms where stretching of proteins results in biological responses. In this work, we present the first cyto-mechanoresponsive surface that mimics such behavior by becoming cell-adhesive through exhibition of arginine-glycine-aspartic acid (RGD) adhesion peptides under stretching. This mechanoresponsive surface is based on polyelectrolyte multilayer films built on a silicone sheet and where RGD-grafted polyelectrolytes are embedded under antifouling phosphorylcholine-grafted polyelectrolytes. The stretching of this film induces an increase in fibroblast cell viability and adhesion.     

PHOTOSENSITIZED OXIDATION OF BIOMATERIALS and RELATED MODEL COMPOUNDS

Aluminium trisulfonatophthalocyanine (A1PCS), a dye being widely advocated for use in photodynamic therapy, produces singlet oxygen with a quantum yield of 0.34 in oxygenated water at pH 7. Triplet A1PCS abstracts an electron from a variety of amines and phenols, the rate of electron transfer depending upon the thermodynamic driving force, forming the A1PCS radical anion. This latter species reduces molecular oxygen to superoxide ions with high efficiency. The triplet state also abstracts an electron from biological components, including NADH, vitamin C, cysteine, methionine, tyrosine, tryptophan, uracil, and guanine, but not from DNA. These results suggest that photoinduced electron abstraction from appropriate biomaterials could compete with singlet oxygen production under in vivo conditions.     

An investigation of the solidification of a metal and two n-paraffins using an acoustic technique

A novel acoustic technique is described for following the motion of the solid-liquid interface during the freezing of mercury, n-hexadecane and n-octadecane where heat transfer is unidirectional. It is shown that the actual amount of solidification occurring in a given time differs from that predicted using a numerical solution to the transient heat conduction problem. The differences are small for mercury but large for the paraffins. They are interpreted in terms of the nature of the solid-liquid interface. Furthermore the experimental and predicted temperature distributions in the liquid and solid phases differ. These differences are extremely small for mercury. The data for the three materials conform to a relationship observed previously according to which the thickness of the solidified layer is a linear function of the square root of time. The work was carried out at the Georgia Institute of Technology.     

High-order sliding-mode observation for linear systems with unknown inputs

A high-order sliding-mode observer is designed for linear systems with unknown inputs. The concepts of strong observability and strong detectability are studied and their relation with the relative degree of a plant is established. High-order sliding-mode-based observers for linear time-invariant systems with unknown inputs satisfying the condition of strong observability or strong detectability are developed.     

PHOTOREACTIONS OF MACROCYCLIC DYES BOUND TO HUMAN SERUM ALBUMIN

The photophysical properties of tetrakis(4-sulfonatophenyl)porphyrin (H2TSPP), its tin (IV) complex (SnTSPP), aluminium(III) trisulfonatophthalocyanine (AIPCS), and the corresponding zinc(II) complex (ZnPCS), have been measured in H2O, D2O, and upon binding to human serum albumin (HSA). The triplet excited states of the various macrocyclic dyes generate singlet molecular oxygen, O2(1 delta g) in high quantum yield upon illumination in O2-saturated solution, even in the presence of HSA. The triplet states also abstract an electron from 4-aminophenol, forming the radical anion of the macrocycle. Quenching rate constants and quantum yields have been measured for the various processes in the presence and absence of HSA. It is found that HSA binds all the dyes at nonspecific sites close to the interface in such a manner that the dyes remain accessible to species residing in the solution phase. Dyes that do not possess axial ligands complexed to the central cation (e.g. H2TSPP, ZnPCS) are able to bind also at a deeper, more specific site on the protein where they are protected from species in solution. Under such conditions, triplet quenching by 4-aminophenol is restricted to long-distance electron tunnelling, for which the rate is relatively slow.