THE EFFECT OF COORDINATING LIGANDS ON THE TRIPLET STATE OF CHLOROPHYLL

Under laser excitation at 457.9 and 514.5 nm, a frozen solution of chlorophyll a in n -octane displays fluorescence peak maxima at 2K that may be assigned to two distinct monomeric chlorophyll species. Using zero-field fluorescence-detected magnetic resonance the triplet state properties of the two chlorophyll species have been assigned to the monoligated and biligated chlorophyll monomer in which water serves as the ligand coordinated to the magnesium metal center. These triplet state properties for chlorophyll in solution are then utilized in interpreting triplet state results for in vivo chlorophylls associated with the light harvesting chlorophyll protein complex. It is shown that the triplet state data are consistent with attachment of the chlorophyll molecule to the protein site with a single ligand coordinated to the chlorophyll metal center.     

The elucidation of the 1H- and 13C-NMR spectra of bis[N,N-di(2,3-epoxypropyl)-4-aminophenyl]methane (TGMDA) and composite with bis(4-animophenyl)sulfone (DDS) using two-dimensional fourier transform techniques

The application of Fourier transform (FT) two-dimensional nuclear magnetic resonance spectroscopy to the study of the composite of bis[N,N-di(2,3-epoxypropyl)-4-aminophenyl] methane (TGMDA) and the curing agent bis(4-aminophenyl)sulfone (DDS) is discussed. The combination of 2D-J resolved and homonuclear (proton) shift correlated experiments permits the complex proton spectrum due to the glycidylamine moiety to be completely elucidated. The potential utility of this in the study of the aging of prepreg is briefly discussed.     

Preparation and mössbauer studies of tetraaquabis[maleato(1-)]-iron(II)

Summary Tetraaquabis[maleato(1-)]iron(II), Fe(C₄H₃O₄)₂ · 4H₂O has been synthesised. The compound is monomeric and is isomorphous with the manganese(II) analogue. The temperature dependence of quadrupole splitting and optical spectral data giveca. 10000 cm^–1,ca. 650 cm^–1,ca. 190 cm^–1 andca. 1400 cm^–1 for the 10 Dq, tetragonal field, rhombic field and the splitting of the E_g level, respectively. The quadrupole splitting data indicate that distortion from cubic symmetry increases in the order oxalate < malonate < maleate. DTA, TGA and Mössbauer studies indicate elimination of one molecule of maleic acid at 235 °C. The resulting product shows a less distorted structure and this is attributed to the formation of maleato(2-)iron(II).     

In recognition of the sixtieth birthday of James K. Knowles

Dedication

In recognition of the sixtieth birthday of James K. Knowles     

Water removal from porous media by gas injection: experiments and simulation

The flow of a saturated gas through a porous medium, partially occupied by a liquid phase, causes evaporation due to gas expansion. This process, referred to as flow-through drying, is important in a wide variety of natural and industrial applications, such as natural gas production, convective drying of paper, catalysts, fuel cells and membranes. X-ray imaging experiments were performed to study the flow-through drying of water-saturated porous media during gas injection. The results show that the liquid saturation profile and the rate of drying are dependent on the viscous pressure drop, the state of saturation of the gas and the capillary characteristics of the porous medium. During the injection of a completely saturated gas, drying occurs only due to gas expansion. Capillary-driven flow from regions of high saturation to regions of low saturation lead to more uniform saturation profiles. During the injection of a dry gas, a drying front develops at the inlet and propagates through the porous medium. The experimental results are compared with numerical results from a continuum model. A good agreement is found for the case of sandstone. The comparison is less satisfactory for the experiments with limestone.     

Evaluation of the role of magnetization transfer imaging in prostate: a preliminary study

Results of the preliminary study on the evaluation of the role of magnetization transfer imaging (MTI) of prostate in men who had raised prostate-specific antigen (PSA) (>4 ng/ml) or abnormal digital rectal examination (DRE) are reported. MT ratio (MTR) was calculated for 20 patients from the hyper- (normal) and hypo-intense regions (area suspicious of malignancy as seen on T2-weighted MRI) of the peripheral zone (PZ) and the central gland (CG) at 1.5 T. In addition, MTR was calculated for three healthy controls. Mean MTR was also calculated for the whole of the PZ (including hyper- and hypo-intense area) in all patients. Out of 20 patients, biopsy revealed malignancy in 12 patients. Mean MTR value (8.29+/-3.49) for the whole of the PZ of patients who were positive for malignancy on biopsy was statically higher than that observed for patients who were negative for malignancy (6.18+/-3.15). The mean MTR for the whole of the PZ of controls was 6.18+/-1.63 and is similar to that of patients who were negative for malignancy. Furthermore, for patients who showed hyper- (normal portion) and hypo-intense (region suspicious of malignancy) regions of the PZ, the MTR was statistically significantly different. These preliminary results reveal the potential role of MT imaging in the evaluation of prostate cancer.     

A Bio-Inspired 128 × 128 Complementary Metal–Oxide–Semiconductor Vision Chip for Edge Detection with Signal Processing Circuit Separated from Photo-Sensing Circuit

In this paper, a vision chip for edge detection based on the structure of biological retina is introduced. The key advantage of retinal structure is speed of operation. However, bio-inspired vision chips have suffered from low resolution which is caused by their complex circuit structure. To sufficiently improve the resolution for real application, the circuits for analog processing were separated from circuits for image capturing. In addition, we compensated the low speed problem of operation which is caused by bottleneck of data transfer between photo-sensors and analog processing circuit by adding a reset decoder. The vision chip was fabricated using 0.35 μm 2-poly 4-metal complementary metal---oxide---semiconductor technology. Using the vision chip, we could obtain a contrast-enhanced image without any other cost-increase for fabrication of chips. Then, the edge image was easily achieved by thresholding the previous contrast-enhanced image.     

Quantum antiferromagnetism in quasicrystals

The antiferromagnetic Heisenberg model is studied on a two-dimensional bipartite quasiperiodic lattice. Using the stochastic series expansion quantum Monte Carlo method, the distribution of local staggered magnetic moments is determined on finite square approximants with up to 1393 sites, and a nontrivial inhomogeneous ground state is found. A hierarchical structure in the values of the moments is observed which arises from the self-similarity of the quasiperiodic lattice. The computed spin structure factor shows antiferromagnetic modulations that can be measured in neutron scattering and nuclear magnetic resonance experiments. This generic model is a first step towards understanding magnetic quasicrystals such as the recently discovered Zn-Mg-Ho icosahedral structure.     

Correlation between a structural parameter and the carboxyl C chemical shielding tensors in compounds containing carboxylic carbon as a functional group

The influence of local molecular geometry on the carboxyl ¹³C chemical shielding tensors in some organic molecules is investigated. The σ₂₂ component of the tensor shows a linear variation as a function of the OCO bond angle around the carboxyl carbon. The significance of the symmetry factors calculated for these compounds is discussed.