Synthesis of 2(r)-[3(s)-acylamino-2-oxo-1 azetidinyloxy]-acetic acids

The title compounds when constructed from a-aminoxyacetic esters coupled with N-benzyloxycarbonyl-L-serine in the presence of N-ethoxycarbonyl-2-ethoxy L-2-(benzyloxyformamido)-3-hydroxypropionamidooxy acetates. Alternative coupling with N-benzyloxycarbonyl-L-serine 3,4-dihydro-4-oxo-l,2,3-benzotriazin triphenyl phosphine and dimethyl azodicarboxylate gave the fully protected monocyclic β-lactams. In the phenylacetic acid series hydrogenolytic deprotection led to decomposition. However, in the phenylpropionic series the hydrogenolysis product was sufficiently stable to allow acylation by the thiol ester route to the title compound.     

PHOTOPHYSICAL STUDIES ON HUMAN RETINAL LIPOFUSCIN

Fluorescent material generated in the human retina accumulates within lipofuscin granules of the retinal pigment epithelium (RPE) during aging. Its presence has been suggested to contributed to various diseases including age-related macular degeneration. Because this material absorbs light at wave lengths as long as 550 nm, photophysical studies were performed to determine whether lipofuscin could contribute to light damage and to determine if its composition is similar to a synthetically prepared lipofuscin. Time-resolved experiments were performed to monitor (1) fluorescence decay, (2) the UV-visible absorption of longer-lived excited states and (3) the formation and decay of singlet oxygen at 1270 nm. Steady-state and time-resolved fluorescence studies indicate that human and synthetic lipofuscin have fluorophores in common. Time-resolved absorption experiments on human retinal lipofuscin and synthetic lipofuscin showed the presence of at least two transient species, one absorbing at 430 nm (lifetime caμs) and a second absorbing at 580 nm, which decays via second order kinetics. In addition, there is a third absorbing species stable to several hundred milliseconds. The transient species at 430 nm is quenched by oxygen, suggesting that it is a triplet state. Subsequent studies showed the formation of singlet oxygen, which was monitored by its phosphorescence decay at 1270 nm. These studies demonstrate that lipofuscin can act as a sensitizer for the generation of reactive oxygen species that may contribute to the age-related decline of RPE function and blue light damage.     

Geminal bis-ureas as gelators for organic solvents: gelation properties and structural studies in solution and in the gel state

Several geminal bis-urea compounds were synthesised by means of an acid-catalysed condensation of various benzaldehydes with different monoalkylureas. Many of these compounds form thermoreversible gels with a number of organic solvents at very low concentrations (<3mM) and which are stable to temperatures higher than 100 degrees C. Electron microscopy revealed a three-dimensional (3D) network of intertwined fibres, which are several tens of micrometers long and have a width ranging from approximately 30 to 300 nm. The possible aggregate forms and aggregate symmetries were evaluated by means of molecular mechanics calculations. 1H NMR, 2D NMR, 13C NMR and 13C-CP/MAS NMR techniques were used to obtain information about the aggregation and possible aggregate symmetry of geminal bis-ureas in solution, in the gel state, and in the solid state.     

An ESR investigation of triple ions derived from 1,2,4,5-tetramesitoylbenzene

Stable triple ions were obtained in MTHF solution from the ion pairs of 1,2,4,5-tetramesitoylbenzene (TMB) radical anion and alkali metal cations by reaction with soluble alkali metal salts. Their ESR spectra are highly resolved. MO calculations with parameters which lead to spin density values as nearly as possible equal to the experimental ones allow estimates of the oxygen-metal distances. The relatively most stable triple ions are the ones with the smallest estimated oxygen metal distances.     

Long-range sigma-pi interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes). Photo-electron spectroscopy, ab initio SCF MO calculations, and natural bond orbital analyses

Long-range sigma-pi interactions in tetrahydro4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Ivj of the highest occupied molecular orbitals (MO's) were assigned using Koopmans' theorem (Iv,j = -epsilonj) and by correlation with the ionizations of related reference compounds. The experimental (PES) and theoretical (RHF/6-31G*) results are in good agreement. For tercyclohexylidene derivatives which contain two nonconjugated pi-bonds splittings deltaIv,j of the pi-bands in the range from approximately 0.5 to 0.7 eV (delta-epsilonj approximately 0.6 to 0.9 eV). For the bi- and tercyclohexylidene compounds containing two sulfur atoms at their alpha- and omega-end positions the pi-type sulfur lone pair bands [Lppi(S)] split significantly by deltaIvj approximately 0.3 to 0.4 eV (delta-epsilonj approximately 0.3 to 0.4 eV), i.e. sigma-pi interactions over distances of ca. 8 and 12 A, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon skeletons. RHF/6-31G* Natural Bond Orbital analyses reveal that the Hax-C-C-Hax precanonical MO's (PCMO's) centered on the cyclohexyl-type rings are paramount for the relay of the through-bond sigma-pi interactions; no through-space sigma-pi interactions were identified.     

AGE-RELATED CHANGES IN THE HUMAN LENS AS MONITORED BY DETECTION OF PORPHYRIN EXCITED STATES

Abstract— Previous studies have shown that the triplet state lifetimes of various porphyrins are increased by several orders of magnitude when they are bound to lens proteins. Flash photolysis studies of me-sotetra ( p -sulfonatophenyl)porphyrin (TPPS) on intact bovine lenses indicated a biexponential decay of the triplet state with lifetimes of 160 μs and 1.6 ms. Here we extend those measurements to TPPS associated with intact human lenses. Steady-state fluorescence measurements indicate that TPPS binds to both young and old human lenses. In an intact young human lens, the TPPS triplet state is observed to decay biexponentially with lifetimes of 50 and 680 μs. As the age of the lens increases, the lifetime of the shorter-lived component lengthens while that of the longer-lived component decreases slightly. In older human lenses, the two lifetimes coalesce and the triplet decay exhibits purely monoexponential behavior. These photophysical characteristics apparently are due to age-related modification(s) of the protein in the human lens resulting in an increasingly more homogeneous environment around the porphyrin.     

Proton hyperfine couplings in VO(H2O)2+5: The validity of the point-dipole approximation

A double-zeta wavefunction has been used to calculate the dipolar electron—proton hyperfine interactions in VO(H₂O)²⁺₅ using numerical integration. The results indicate that a point-dipole model is a good approximation for this ion.     

Dielectric analysis of the interaction of nematic liquid crystals with carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) have been shown to self-organise, and when added as a guest to form a nanocomposite, their director couples with an organic liquid crystal (LC) host. Here, effects of MWCNTs on the low-frequency dielectric properties and Fréedericksz transition of the LC 4-cyano-4?-pentylbiphenyl (5CB) are studied. Anti-parallel electro-optic cells were filled with nanocomposites at weight percent concentrations of MWCNT to 5CB of: 0 (neat), 0.01, 0.10, 0.20, and 0.50. Low concentration was chosen to minimise Van der Waals attraction normally responsible for aggregation of MWCNTs. Dielectric relaxation spectroscopy was used to study interactions between MWCNTs and 5CB at frequencies from 20 Hz to 1 MHz. We propose a mechanism based upon measurements of the complex dielectric function which suggests that MWCNTs act as a slow-moving boundary within the sample cell at low frequencies and low applied electric fields, where the MWCNTs reorient along with the 5CB LC molecules. At higher frequencies and larger applied electric fields, the 5CB molecules rotate about their long axes while motion of the MWCNTs is frozen out.