Photophysical Studies of A2-E, Putative Precursor of Lipofuscin, in Human Retinal Pigment Epithelial Cells

With age, human retinal pigment epithelial cells accumulate lipofuscin that can absorb photons in the visible range leading to light-induced damage and impaired vision. A putative precursor of lipofuscin, 2-[2,6-dimethyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1E,3E, 5E,7E- octatetraenyl]-1-(2-hydroxyethyl)-4-[4-methyl-6-(2,6,6-trimethyl-1 - cyclohexen-1-yl)-1E,3E,5E-hexatrienyl]-pyridinium (A2-E), has recently been isolated and characterized from aged human retinal pigment epithelial cells. We have found that A2-E inhibits the growth of human retinal pigment epithelial cells at concentrations greater than 1 microM. Time-resolved fluorescence measurements of 1 microM A2-E in solution, performed under 413 nm excitation, showed that fluorescence wave forms integrated across the spectrum (450-600 nm) were best-fitted with three decay times in the nanosecond and subnanosecond time scale: 6.6, 1.9 and 0.33 ns. Untreated retinal pigment epithelial cells were characterized by three fluorescence lifetimes: 6.3, 1.7 and 0.35 ns. In retinal pigment epithelial cells treated with 1 microM A2-E, the fluorescence decay was significantly faster, with the marked presence (approximately equal to 30%) of a fourth short lifetime (0.12 ns). These fluorescence decay times for A2-E bound to human retinal pigment epithelial cells are similar to those of lipofuscin granules isolated from aged human retinal pigment epithelial cells. This similarity supports the hypothesis that A2-E is a precursor of lipofuscin and suggests that A2-E may play a role in the overall light damage associated with age-related retinal diseases.     

Solution and Solid‐State Analysis of Binding of 13‐Substituted Berberine Analogues to Human Telomeric G‐quadruplexes

The interaction between 13‐phenylalkyl and 13‐diphenylalkyl berberine derivatives ( NAX ) and human telomeric DNA G4 structures has been investigated by both spectroscopic and crystallographic methods. NAX042 and NAX053 are the best compounds improving the performance of the natural precursor berberine. This finding is in agreement with the X‐ray diffraction result for the NAX053 ‐Tel12 adduct, showing the ligand which interacts via π‐stacking, sandwiched at the interface of two symmetry‐related quadruplex units, with its benzhydryl group contributing to the overall stability of the adduct by means of additional π‐stacking interactions with the DNA residues. The berberine derivatives were also investigated for their cytotoxic activity towards a panel of human cancer cell lines. Compounds NAX042 and NAX053 affect the viability of cancer cell lines in a dose‐dependent manner.     

On the Energetics of Ions in Carbon and Gold Nanotubes

We investigate the insertion of halide and alkali atoms into narrow single‐walled carbon nanotubes with diameters <9 Å by density functional theory; both chiral and non‐chiral tubes are considered. The atoms are stored in the form of ions; the concomitant charge transfer affects the band structure and makes originally semiconducting tubes conducting. The electrostatic interaction between a charge and the walls of the tube is explicitly calculated. The insertion energies and the positions of the ions are determined by a competition between electrostatic energy and Pauli repulsion. For comparison, we consider ions in gold nanotubes. Alkali ions follow the same principles in gold as in carbon tubes, but chloride is specifically adsorbed inside gold tubes.     

Calorimetric analyses on aged Al–4.4Cu–0.5Mg–0.9Si–0.8Mn alloy (AA2014 grade)

An Al–4.4Cu–0.5Mg–0.9Si–0.8Mn alloy (IADS 2014 grade) in the solution annealed and peak aged condition was exposed at 170°C for relatively long times (up to about 1800 h) in order to check the stability of the alloy. The investigated aging temperature was in the frame of a research on the long-term mechanical behaviour of such alloy. Microstructure evolution was monitored via calorimetric analyses, metallographic inspections and hardness measurements. Further, X-ray analyses were carried out on selected samples. The attention was focused on differential scanning calorimetry performed at different scanning rates, with the aim of evaluating the kinetics of the precipitation phenomena. Notwithstanding the wide industrial diffusion of this alloy, literature survey showed that there is not a consensus view on the precipitation sequences and on calorimetric peak identification. The present results show the progressive evolution of calorimetric peaks, corresponding to that of strengthening particles towards more stable phases, proved by the disappearance of exothermic peaks. Activation energy from Kissinger kinetic analysis in the case of aged samples provided scattered values that could be reasonably attributed to an overlapping of transformation peaks. Moreover, in these samples transformations partially occurred before DSC scans, providing non-constant transformation fraction at signal peak temperatures and resulting in different activation energies.     

Unsaturated alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s: Synthesis and chemical–physical characterization

A new series of alkoxy‐substituted poly(p‐phenylene 1,3,4‐oxadiazole)s modified by the insertion of small percentages of various comonomers were synthesized through the precursor polyhydrazides. The comonomers used contained trans double bonds or meta‐alkoxy‐substituted aromatic rings to improve the solubility of the final polymers. The synthesized copolymers were chemically characterized by ¹H NMR and Fourier transform infrared spectroscopy. In some cases, the copolymers really showed improved solubility in organic solvents. The ¹⁵N solid‐state NMR technique was applied to examine the degree of conversion from the precursor polyhydrazides to the final polymers, which determined the effective conjugated length in the target polyoxadiazoles. Thermal stability and structural characteristics of all the polymers as well as a preliminary investigation on the optical properties of polyoxadiazoles are also reported. The copolymers retained high absorbance in the UV region and high transmission in the whole telecommunication range. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3916–3928, 2003     

Ru2+ complexes comprising terpyridine ligands appended with terthiophene chromophores: energy transfer and energy reservoir effect

Two Ru(2+) complexes containing terpyridine ligands appended with terthiophene units connected by a methyleneoxy or an alkynyl bridge show very different luminescent behaviours: the former is non-luminescent at 298 K owing to a photoinduced energy transfer process to the terthiophene moiety, while the latter exhibits an extraordinary long excited state lifetime because of an energy reservoir effect.     

Charge-assisted hydrogen bond-directed self-assembly of an amphiphilic zwitterionic quinonemonoimine at the liquid-solid interface

Charge-assisted hydrogen bond-directed self-assembly of a zwitterionic quinonemonoimine was investigated at the liquid/solid interface using scanning tunnelling microscopy. Factors governing morphology, chirality and multilayer formation are discussed, presenting an important foundation for understanding the properties of a large family of related molecules with interesting potential in supramolecular design.     

Are electrophilicity and electrofugality related concepts? A density functional theory study

It is proposed that the electrofugality of a fragment within a molecule is determined by its group nucleophilicity. The variation of electrofugality should be tightly related to the electron releasing ability of the substituent attached to the electrofuge moiety. This contribution closes the set of relationships between philicity and fugality quantities: while nucleofugality appears related to the group electrophilicity of the leaving group, electrofugality is related to the group nucleophilicity of the permanent group.