THE MECHANISM OF PHOTOSENSITIZATION IN PHOTODYNAMIC THERAPY: PHOSPHORESCENCE BEHAVIOR OF PORPHYRIN DERIVATIVES IN SALINE SOLUTION CONTAINING HUMAN SERUM ALBUMIN

The phosphorescence properties, especially the dynamic behavior of metal free and metal complexed porphyrins, have been studied in phosphate buffered saline (PBS) containing 0-3% human serum albumin (HSA). 6,7-Bisaspartyl-2,4-bis (1-hexyloxyethyl)-deutero- porphyrin (DP) and its gallium(III), zinc(II), and indium(III) complexes are used as photosensitizers. Upon irradiation, a solution of porphyrins containing more than 0.1% HSA shows phosphorescence with a lifetime longer than 1 ms. With an increase in irradiation time, phosphorescence intensities and lifetimes of porphyrins increase, depending upon their concentrations and triplet lifetimes, and approach saturated values close to those under deaerated conditions. The experimental results may be interpreted in terms of hypoxia induced by photosensitization in a local environment surrounding the sensitizer. The hypoxia is caused by the reaction between proteins and singlet molecular oxygen generated by photosensitization of porphyrins. Phosphorescence behavior of sensitizers in HSA PBS solution gives significant information for classifying photosensitizers as to their efficacy for photodynamic therapy.     

Pressure-induced structural phase transition of iodine

The structural phase transition of iodine was observed at about 210 kbar and at room temperature by the high-pressure x-ray diffraction technique using a diamond-anvil cell and a position-sensitive detector. It was found to occur reversibly in both processes of increasing and decreasing pressure.     

Two new dimeric acridone alkaloids from Glycosmis citrifolia

Two new acridone dimers, glycobismines-F (1) and -G (2), were isolated from the roots of Glycosmis citrifolia collected in Taiwan. The structures of the new compounds were determined based on spectral analysis.     

Some characterizations of minimal Markov basis for sampling from discrete conditional distributions

In this paper we given some basic characterizations of minimal Markov basis for a connected Markov chain, which is used for performing exact tests in discrete exponential families given a sufficient statistic. We also give a necessary and sufficient condition for uniqueness of minimal Markov basis. A general algebraic algorithm for constructing a connected Markov chain was given by Diaconis and Sturmfels (1998,The Annals of Statistics,26, 363–397). Their algorithm is based on computing Gröbner basis for a certain ideal in a polynomial ring, which can be carried out by using available computer algebra packages. However structure and interpretation of Gröbner basis produced by the packages are sometimes not clear, due to the lack of symmetry and minimality in Gröbner basis computation. Our approach clarifies partially ordered structure of minimal Markov basis.     

Complexes of ytterbium(III) nitrate and triflate with homoazacalix[n]arenes (n=3, 4)

The synthesis and crystal structures of three ytterbium(III) complexes of homoazacalixarenes are reported. In all cases, the complexes are obtained without addition of a base, the protons of the complexing phenolic moieties being transferred to the amine groups upon complexation. The 1:1 complex between p-chloro-N-benzylhexahomotriazacalix[3]arene (1) and Yb(NO₃)₃ is analogous to the neodymium(III) complex reported previously, with the metal ion bound to three phenoxide groups and three nitrate ions. A second 1:1 complex is obtained with Yb(NO₃)₃ and p-methyl-N-benzyltetrahomodiazacalix[4]arene (2), in which the metal ion is bound to two phenoxide groups only. The replacement of nitrate by triflate counter-ions results in the formation of a 1:2 ‘sandwich’ complex with 1, in which two divergent calixarene molecules are bridged by the metal ion, the counter-ions being non-bonding.     

Controlling the thermomechanical properties of biobased ABA triblock copolymers comprising polylactide (A) and poly(1,2-propylene succinate) (B) with high molecular weight

Bis-hydroxyl-terminated poly(1,2-propylene succinate) (PPS-diols) with high molecular weight (10–40 kDa) are prepared by two-step melt polycondensation of succinic acid and 1,2-propanediol with Ti(BuO)₄ as the catalyst. By using these PPS-diols as macroinitiators, the ring-opening polymerization of d - and l -lactides is readily conducted to obtain enantiomeric ABA triblock copolymers consisting of poly(l -lactide) and PPS (B) (t-l -PPS) as well as those of poly(d -lactide) and PPS (B) (t-d -PPS) which have higher PPS compositions (20–70 wt%) in addition to high molecular weight (20–80 kD). The T_g, T_m, and ΔH_m values of the t-l -PPS copolymers as well as the stereo mixtures of t-l -PPS/t-d -PPS are controlled to linearly decrease with increasing the PPS content. The copolymers also exhibit higher elastomeric properties with increasing the PPS content. The tensile properties of the copolymer films having higher PPS contents (both the single block copolymers and stereo mixtures) are comparable to those of the oil-based thermoplastic elastomers. It is therefore concluded that these block copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% biobased content.     

Real-root property of the spectral polynomial of the Treibich–Verdier potential and related problems

We study the spectral polynomial of the Treibich–Verdier potential. Such spectral polynomial, which is a generalization of the classical Lamé polynomial, plays fundamental roles in both the finite-gap theory and the ODE theory of Heun's equation. In this paper, we prove that all the roots of such spectral polynomial are real and distinct under some assumptions. The proof uses the classical concept of Sturm sequence and isomonodromic theories. We also prove an analogous result for a polynomial associated with a generalized Lamé equation, where we apply a new approach based on the viewpoint of the monodromy data.     

Microrheology of polysaccharide nanogel-integrated system

The viscoelastic behavior of a cholesterol-modified pullulan (CHP) nanogel at various concentrations was measured using passive particle-tracking microrheology. Microrheology measures stress–strain relationships in small volumes of material by monitoring the response of probes embedded in the medium. Although microrheology is a useful way to overcome sample volume limitations, the application of the method to CHP nanogel systems has not been reported. The viscoelastic spectra of the CHP nanogels obtained from the microrheological measurements were in good agreement with the bulk rheological measurements for each sample, demonstrating that microrheological measurement is effective in CHP nanogel systems. The gelation behavior of CHP nanogel dispersions containing pullulans of different molecular weights was also investigated by microrheology. CHP nanogels made from 1.0 or 4.0?×?10⁵ molecular weight pullulans formed a macrogel at around 3.0 wt%, whereas the CHP nanogel consisting of 0.55?×?10⁵ molecular weight pullulan did not form a macrogel. This suggests that the mechanical properties of the system can be controlled by the molecular weight of the pullulan used. These insights into gelation behavior should be useful in predicting the most favorable conditions for developing novel materials.