INTRAVENOUS vs INTRAPERITONEAL SENSITIZER: IMPLICATIONS FOR INTRAPERITONEAL PHOTODYNAMIC THERAPY

Photodynamic therapy (PDT) is a potential treatment for peritoneal carcinomatosis. However, little data is available regarding the relative distribution of sensitizer to tumor and intra-abdominal organs, optimal route of sensitizer administration, and maximal tolerated light dose. Tumor and normal tissue sensitizer levels were measured by tissue extraction 3, 24, 48 and 72 h after 10 mg/kg of Photofrin II was given intraperitoneally (IP) or intravenously (IV) in a mouse peritoneal tumor model, and the maximal tolerated PDT light dose determined. Equivalent tumor sensitizer levels were obtained regardless of the route of sensitizer administration. Route of administration, however, did affect the kinetics of tumor sensitizer elimination, with the half-time for elimination (T1/2) 113.6 h for IP drug and 60.6 h for IV drug. Route of administration also affected sensitizer levels in several intra-abdominal organs, resulting in somewhat higher tumor to liver and kidney levels at 24 and 72 h after IP sensitizer administration. Despite these tissue distribution differences, route of sensitizer administration did not significantly affect PDT toxicity or mortality when mice were treated with 630 nm light. The maximum tolerated light dose was 1.04 J/cm2. These parameters will prove helpful in designing large scale animal trials assessing the efficacy and safety of intra-abdominal PDT.     

The free energy differences between 3-point water models

(Molecular Physics, 1998, 94, 717–725)     

Microwave and infrared spectroscopy of the CH4—OCS complex

Pulsed molecular beam spectra of the CH₄-OCS complex have been recorded using both a molecular beam infrared diode laser and a Fourier transform microwave spectrometer. Analysis of the spectrum yields a near T shape structure with a centre of mass separation of 3.83 Å and a CH₄ centre of mass-OCS centre of mass-oxygen angle of 73°. Splittings attributed to the internal rotations of methane within the complex have been observed in the microwave spectrum. The rotational constants of the complex for the A and T librational states of CH₄ were determined. The differences (T-A) in the rotational constants were ΔA = 0.35, ΔB = ?1.60 and ΔC = ?1.85 kHz.     

Magnetic field dependence of the deactivation rates of triplet azocumene in solution

The triplet sensitized photo-decomposition of azocumene into nitrogen and cumyl radicals is investigated by time resolved EPR and optical absorption spectroscopy. It is found that the cumyl radicals carry an initial spin polarization and are formed with a yield that depends on both the solution viscosity and the strength of an external magnetic field. The phenomenon is interpreted in terms of a depopulation-type triplet mechanism, i.e. a competition between decay into radicals and fast, triplet sublevel selective intersystem crossing (ISC) back to the azocumene ground state. Analysis of the data yields relative rate constants for the ISC processes and the cleavage reaction of triplet azocumene. The energetically lower zero field triplet substate is depopulated by ISC about seven times faster than the upper one and about two orders of magnitude faster than depopulation by cleavage occurs. Cleavage probably takes place on the nanosecond time scale, while the ISC must proceed on the picosecond scale, as at elevated viscosity it becomes faster than the rotational Brownian motion of the molecule.     

Induced moment due to perpendicular field cycling in trained exchange bias system

Depth-sensitive polarized neutron scattering in specular and off-specular mode has recently revealed that perpendicular field cycling brings about a modification in the interfacial magnetization of a trained exchange coupled interface. We show here by various model fits to our neutron reflectivity data that a restoration of the untrained state is not possible in the case of our polycrystalline multilayer specimen. This is due a magnetic moment at the interface induced only after perpendicular field cycling, changing the initial field-cooled state.     

Phase separation in mixtures of colloidal platelets and non-adsorbing polymer: a scaled particle treatment

Scaled particle theory is used to calculate the equation of state for and the free volume accessible to a non-adsorbing polymer, represented by spheres, in a system of colloidal platelets, represented by cut spheres. At low densities the predictions agree very well with computer simulations. For infinitely thin discs, the predictions agree with existing simulation data for the isotropic phase. The analytical results are used to predict the isotropic-isotropic phase boundary as a function of platelet aspect ratio and polymer/colloid size ratio.     

A unified description of MCI3 systems with a polarizable ion simulation model

Computer simulations of a range of ionic systems of stoichiometry MX₃ using a polarizable, formal charge ionic interaction model are described. The objective of the present work is to describe the optimization of the interaction potentials in the light of new structural information which has become available from neutron scattering studies of the liquid. As well as substantially improving the agreement with experiment for LaC1₃, TbC1₃, YC1₃ and A1C1₃, simulation results are presented for the first time for ScC1₃, which is shown to exhibit a fascinating crosslinked network structure. The optimization of potentials for the crystal structures is also considered. It is shown that the C1^? ion must be considered as of smaller size in the crystal than in the liquid in order to successfully reproduce the properties of both phases.     

DYNAMIC LINEAR DICHROISM IN CHROMOPROTEINS

The time-dependent polarized fluorescence and optical density transients arising from electronic excitation transport are derived for solutions of randomly oriented chromoproteins in which the chromophore transition moments have well-defined orientations with respect to the protein. The treatment is extended to oriented monolayers of chromoproteins, in which the molecules are aligned with a particular protein-fixed axis perpendicular to the surface plane and with random azimuthal angles about the surface normal. The initial ratio of parallel to perpendicular transients is invariably 3:1, irrespective of system dimensionality and chromophore organization. The residual anisotropy observed at long times is directly related to the relative orientations of the donor and acceptor chromophores. These calculations form a basis for detailed interpretation of ultrafast fluoresence and pump-probe linear dichroism studies in photosynthetic systems, for which 3-dimensional structures are becoming increasingly available.     

Magnetic field and spin effects from sequential p-type and d-type triplet mechanisms

CIDEP signals of semireduced thionine radicals produced by reacting thionine triplets with aniline and halogenated anilines were measured by time resolved CW and pulsed FT EPR. For aniline as quencher, the polarization was emissive while for 4-Br- and 3-I-aniline a time dependent change in polarization from emissive to enhanced absorption was observed. For 4-I-aniline the signals were in enhanced absorption for all delay times. The time and concentration dependence of the signals was analysed in terms of a sequential double triplet mechanism: polarization of the thionine triplet due to selective population of the molecular triplet substates (classical ‘p-type’ triplet mechanism) and modification of this polarization by substate selective, heavy atom induced depopulation of triplet exciplexes (triplet contact radical pairs) formed as intermediates in the triplet quenching by electron transfer (‘d-type’ triplet mechanism). A quantitative theoretical treatment that combines the time-integrated solution of the stochastic Liouville equations for precursor triplet and triplet exciplex with the kinetic rate equation of the bimolecular quenching process is presented. The equations derived allow the extraction of two polarization enhancement factors, V _d for the pure d-type and V _pd for the combined p- and d-type triplet mechanism from the concentration dependence of the time dependent CIDEP signals. The CIDEP curves and the previously observed magnetic field and heavy atom effects on the free radical yield can be quantitatively simulated with a consistent set of kinetic parameters.