ADRIAMYCIN RESISTANCE IN CHINESE HAMSTER FIBROBLASTS FOLLOWING OXIDATIVE STRESS INDUCED BY PHOTODYNAMIC THERAPY

Photodynamic therapy (PDT) generates reactive oxygen species that are responsible for the initial cytotoxic events produced by this treatment. An extended (16 h) porphyrin incubation prior to light irradiation increased expression of the 75, 78 and 94 kDa glucose-regulated stress proteins (GRP), as well as the cognate form of the 70 kDa heat shock protein. However, these stress proteins were not induced following isoeffective PDT doses using a short (1 h) porphyrin incubation protocol. In the current study, Chinese hamster fibroblasts were used to examine sensitivity to adjunctive PDT and adriamycin as previous reports indicate a correlation between stress protein synthesis and a decrease in adriamycin cytotoxicity. Treatments that either induced GRP ( i.e . PDT with an extended porphyrin incubation or exposure to the calcium ionophore A23187) or did not induce GRP ( i.e . PDT with a short porphyrin incubation or UV irradiation) were followed at increasing time intervals with a 1 h adriamycin incubation. A time-dependent decrease in adriamycin cytotoxicity was observed when cells were first exposed to either of the PDT protocols or to A23187. Alterations in intracellular drug levels did not account for the change in adriamycin sensitivity. Likewise, intracellular glutathione concentrations and antioxidant enzyme activities were not significantly altered following PDT or A23187. Parameters associated with altered adriamycin sensitivity included a decrease in the percentage of S phase cells following PDT and A23187 as well as a depletion of intracellular ATP after PDT using the extended porphyrin incubation. These results demonstrate that PDT can be added to the growing list of diverse stresses producing transient resistance to adriamycin and that stress protein induction is not universally associated with all oxidative treatments inducing this resistance.     

Synthesis of (chlorovinyl)cobaloxime complexes,model complexes of proposed intermediates in the B12-catalyzed dehalogenation of chlorinated ethylenes

(Chlorovinyl)cobaloxime complexes, (dmgH)2(py)CoR (R = cis-dichlorovinyl, trans-2-chlorovinyl or 1-chlorovinyl, dmgH = dimethylglyoximate) were synthesized from the reaction of chlorinated ethylenes with in situ generated (dmgH)2Co(I) in the presence of pyridine.     

The isomerization of optically-active propargyl alcohols to terminal acetylenes.

The isomerization of optically-active secondary propargyl alcohols, RCHOHCC(CH₂)_nCH₃, to terminal acetylenic alcohols, RCHOH(CH₂)_n+1 C=CH, by potassium 3-aminopropylamide (KAPA) proceeds without loss of configuration at the hydroxy center.     

Characterization of SiO2 protective coatings on polycarbonate

SiO₂ protective coatings have been deposited on polycarbonate substrates by plasma ion assisted deposition. The influence of ion energy on the water permeability and the surface topography of the coatings was studied by infrared spectroscopy and atomic force microscopy. Coatings deposited at sufficiently high ion energies show a barrier effect against moisture uptake and considerably reduced film roughness. Both effects are attributed to an increase of the packing densities of the coatings.     

The alpha-helix folds more rapidly at the C-terminus than at the N-terminus

The helix-coil dynamics of different sections of an alpha-helical model peptide were observed separately by nanosecond temperature jump experiments with IR detection on a series of isotopically labeled peptides. The results show that the helix-coil dynamics of the alpha-helical C-terminus are faster than those of the N-terminus.     

Production of octadienal in the marine diatom Skeletonema costatum

[reaction: see text] Marine diatoms produce alpha,beta,gamma,delta-unsaturated aldehydes that have detrimental effects on the reproduction of their natural predators. The production of these defensive metabolites is suggested to involve enzymatic oxidation of polyunsaturated fatty acids. In this paper, feeding experiments with labeled precursor provide clear evidence in support of the origin of octadienals 1 and 2 from 6,9,12-hexadecatrienoic acid (5), thus proving the involvement of novel lipoxygenase/lyase activity for the oxidation of C(16) fatty acids.     

A preliminary observation of additive thermodynamic contribution of pendant arms to the complexation of calixarene derivatives with mercury(II)

An additive thermodynamic contribution of pendant arms to the complexation of calixarene derivatives with mercury(II) in acetonitrile is for the first time demonstrated.     

Central polynomials and matrix invariants

LetK be a field, charK=0 andM _n (K) the algebra ofn×n matrices overK. If λ=(λ₁,…,λ _m ) andμ=(μ ₁,…,μ _m ) are partitions ofn ² let wherex ₁,…,x _n ²,y ₁,…,y _n ² are noncommuting indeterminates andS _n ² is the symmetric group of degreen ². The polynomialsF ^{λ, μ} , when evaluated inM _n (K), take central values and we study the problem of classifying those partitions λ,μ for whichF ^{λ, μ} is a central polynomial (not a polynomial identity) forM _n (K). We give a formula that allows us to evaluateF ^{λ, μ} inM(K) in general and we prove that if λ andμ are not both derived in a suitable way from the partition δ=(1, 3,…, 2n−3, 2n−1), thenF ^{λ, μ} is a polynomial identity forM _n (K). As an application, we exhibit a new class of central polynomials forM _n (K). In memory of Shimshon Amitsur Research supported by a grant from MURST of Italy.     

Thermal decomposition of lignocellulosic materials: comparison of the results obtained in different experimental systems

An experimental system that allows the use of large particle sizes and the simulation of different operating conditions was built to study the thermal decomposition of lignocellulosic materials. The values of solid conversion and of temperature obtained at different points using spherical particles of pine wood 2 cm in diameter are shown. The conversion values are compared with those calculated from the equations obtained in a thermobalance for small particle sizes.     

Recognition of guests bearing donor and acceptor hydrogen bonding groups by heteroditopic calix[4]arene receptors

The synthesis of new hosts specifically designed for the recognition of neutral guests bearing donor-acceptor hydrogen bonding groups is described. These hosts are characterized by the presence of two distinct binding region in close proximity: the rigid π-donor cavity and the H-bond donor N-methylene-N′-phenylureido group inserted onto the upper rim of the calix[4]arene skeleton. The binding abilities of these receptors were investigated toward a series of neutral ditopic organic molecules in CDCl₃ solution by ¹H NMR spectroscopy. The results obtained show that rigidity of the calix[4]arene apolar cavity is the control element in determining efficiency. In fact, compared with the more rigid 2, host 10, where the rigidity of the cone structure is maintained by hydrogen bonding of the OH of the lower rim, a decrease of efficiency of almost one order of magnitude was observed. The cooperative effect of the two binding region of host 2 was verified with different classes of ditopic guests. Good efficiency in the recognition of urea derivatives and dimethylsulfoxide was achieved.