Nucleotide oxidation mediated by naphthalimide excited states with covalently attached viologen cosensitizers

The ground- and excited-state interactions of polymethylene-linked 1,8-naphthalimide-viologen dyads with calf-thymus DNA have been investigated. By virtue of the covalently attached viologen, the compounds represent the first example of linked chromophore/cosensitizer systems in the photooxidation of duplex DNA. The compounds associate strongly with DNA. Analysis of ground-state spectral changes yield binding constants of 0.7-2.5 x 10(6) M-1. Upon 355 nm pulsed irradiation of the compounds in the presence of calf-thymus DNA, reduced viologen is observed within the laser pulse. Photoproducts are not observed on this time scale in the absence of DNA. Since ground-state bleaching of the naphthalimide was not observed, the results suggest that DNA nucleobases are the species being oxidized. The quantum efficiency of radical production increases with the extent of binding to DNA. Under conditions where the compounds are bound predominantly to DNA, the quantum efficiencies were found to range from 0.02 to 0.03. Although small, the values represent a substantial increase in charge-separation yield compared to 1,8-naphthalimide compounds that lack the covalently attached viologen. The mechanism of radical production and effect of number of intervening methylenes are discussed.     

Laser-induced phase explosion: new physical problems when a condensed phase approaches the thermodynamic critical temperature

Three kinds of thermal processes may lead to material loss from a laser-irradiated surface: 1) vaporization, 2) normal boiling, and 3) explosive boiling. The latter is equivalent to phase explosion. It is appropriate, at this point, to exclude "subsurface heating", as there are strong doubts about its existence. The relevance of the three processes depends on the laser pulse duration as well as on the temperature attained in the irradiated zone. We revisit the three thermal processes by noting that: 1) vaporization is not important for the shortest time-scales (<1 ns). 2) Normal boiling is subject to a major kinetic obstacle in the process of bubble diffusion, such motion being sufficiently slow that it will simply not occur for t<100 ns. This is because the value of the bubble diffusion coefficient leads to distances traveled which are atomically small for both 1 ns and 100 ns, and for both T=T_m and T=2T_m, with T_m being the melting temperature. 3) Phase explosion, notwithstanding the unfavorable time-scale (1-100 ns) advocated by Martynyuk, as carefully analyzed in this paper, is found to be the most efficient mechanism in the ablation process when looking at thermal processes. Here it should be recognized that a new field in the physics of condensed matter may be emerging when looking at physical properties near the thermodynamic critical temperature, T_tc. In fact, laser irradiation experiments probably represent a unique tool to investigate matter under extreme thermodynamic conditions and on very short time-scales (ps or fs).     

Modulus and yield resistance of glassy blends containing diluents manifesting varying degrees of mobility: Polyphenylene ether/polystyrene/diluent mixtures

The glass temperatures, moduli, and yield stresses for shear failure have been characterized for homogeneous blends of poly(2,6-dimethyl-1,4-phenylene ether), homopolystyrene (1/1), and a number of diluents of T_gs from ?134 to +32°C. In a blend series based of a given diluent, the mechanical properties vary with blend T_g at rates that are characteristics of the particular diluent. These characteristic rates are found to depend strongly on the T_g of the neat diluent. Thus, for blends all with T_g = 90°C, for example, modulus and yield stress differ by as much as 50% over the range of diluents. Low-temperature relaxation measurements together with a number of previous dynamic spectroscopy studies of polymer/diluent systems at low temperatures suggest that many single-phase polymer/diluent blends may exhibit two primary relaxations—the depressed alpha relaxation of the resin and a somewhat elevated alpha relaxation of the diluent—at quite different temperatures. Both of these relaxations influence stiffness and strength properties at intermediate temperatures. The often-studied antiplasticization phenomena are viewed as a aberrations from a much more general influence of plasticizers on properties at temperatures below the alpha relaxation of the resin.     

Echolocation signals of free-ranging killer whales (Orcinus orca) and modeling of foraging for chinook salmon (Oncorhynchus tshawytscha)

Fish-eating "resident"-type killer whales (Orcinus orca) that frequent the coastal waters off northeastern Vancouver Island, Canada have a strong preference for chinook salmon (Oncorhynchus tshawytscha). The whales in this region often forage along steep cliffs that extend into the water, echolocating their prey. Echolocation signals of resident killer whales were measured with a four-hydrophone symmetrical star array and the signals were simultaneously digitized at a sample rate of 500 kHz using a lunch-box PC. A portable VCR recorded the images from an underwater camera located adjacent to the array center. Only signals emanating from close to the beam axis (1185 total) were chosen for a detailed analysis. Killer whales project very broadband echolocation signals (Q equal 0.9 to 1.4) that tend to have bimodal frequency structure. Ninety-seven percent of the signals had center frequencies between 45 and 80 kHz with bandwidths between 35 and 50 kHz. The peak-to-peak source level of the echolocation signals decreased as a function of the one-way transmission loss to the array. Source levels varied between 195 and 224 dB re: 1 microPa. Using a model of target strength for chinook salmon, the echo levels from the echolocation signals are estimated for different horizontal ranges between a whale and a salmon. At a horizontal range of 100 m, the echo level should exceed an Orcinus hearing threshold at 50 kHz by over 29 dB and should be greater than sea state 4 noise by at least 9 dB. In moderately heavy rain conditions, the detection range will be reduced substantially and the echo level at a horizontal range of 40 m would be close to the level of the rain noise.     

Honulactones: new bishomoscalarane sesterterpenes from the Indonesian sponge Strepsichordaia aliena

From the dichloromethane/2-propanol (1:1) extract of the Indonesian marine sponge Strepsichordaia aliena, twelve new 20, 24-bishomoscalarane sesterterpenes, honulactones A-L (1-12) were isolated. Molecular structures were secured by spectroscopic methods, accurate mass measurements, and X-ray analysis. Honulactones A (1), B (2), C (3), and D (4) exhibit cytotoxycity against P-388, A-549, HT-29, and MEL-28 (IC(50) 1 microg/mL).     

Externalities and the possibility of pareto- satisfactory decentralization

This paper shows that the (New)² Welfare Economics provides interesting new ways of classifying externalities in terms of the complexity of messages required to equate equilibria and optima; and in which, at the end, it is shown that the study of externalities provides useful new insights into the (New)² Welfare Economics by showing problems with the definition of satisfactory informationally decentralized resource allocation mechanisms.