Y-shaped two-photon absorbing molecules with an imidazole-thiazole core

Two new classes of two-photon absorbing Y-shaped molecules have been developed to possess an imidazole-thiazole core and a stilbene-type conjugation pathway with either nitro or sulfonyl as terminal electron-accepting group.     

Seasonal fluctuation of DNA photodamage in marine plankton assemblages at Palmer Station, Antarctica

Ultraviolet radiation-induced DNA damage frequencies were measured in DNA dosimeters and natural plankton communities during the austral spring at Palmer Station, Antarctica, during the 1999-2000 field season. We found that the fluence of solar ultraviolet-B radiation (UV-B) at the earth's surface correlated with stratospheric ozone concentrations, with significant ozone depletion observed because of "ozone hole" conditions. To verify the interdependence of ozone depletion and DNA damage in natural microbial communities, seawater was collected daily or weekly from Arthur Harbor at Palmer Station, Antarctica, throughout "ozone season," exposed to ambient sunlight between 0600 and 1800 h and fractionated using membrane filtration to separate phytoplankton and bacterioplankton populations. DNA from these fractions was isolated and DNA damage measured using radioimmunoassay. Under low-ozone conditions cyclobutane dimer concentrations in bacterioplankton and phytoplankton communities were maximal. DNA damage measured in dosimeters correlated closely with ozone concentrations and UV-B fluence. Our studies offer further support to the theory that stratospheric deozonation is detrimental to marine planktonic organisms in the Southern Ocean.     

Development and application of a novel immunoassay for measuring oxidative DNA damage in the environment

We developed a facile, cost-effective competitive binding assay for the analysis of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) in DNA, using a polyclonal rabbit antiserum raised against an 8-oxodGuo hapten coupled to bovine serum albumin and radiolabeled synthetic ligand containing multiple 8-oxodGuo residues. This radioimmunoassay (RIA) displays a high affinity for 8-oxodGuo in DNA, with a detection limit of approximately 1 adduct in 10(5) bases of DNA. 8-oxodGuo standards for RIA were quantified by high-performance liquid chromatography and electrochemical detection in DNA diluted in methylene blue and exposed to visible light. As an initial application we quantified 8-oxodGuo in dosimeters deployed at increasing depths in the Southern Ocean during the austral spring of the 1998 field season or at the surface at Palmer Station, Antarctica, throughout the 1999 field season. Cyclobutane pyrimidine dimers (CPD) were quantified using an established RIA. We found that the frequency of both photoproducts decreased with depth. However, CPD induction was attenuated at a faster rate than 8-oxodGuo, correlating with the differential attenuation of solar ultraviolet wavelengths in the water column. CPD induction was closely related with ultraviolet-B radiation (UVB) attenuation, whereas the lower attenuation of 8-oxodGuo suggests that oxidative damage is more closely related to ultraviolet-A radiation (UVA) irradiance. The ratio of 8-oxodGuo: CPD was also found to covary with changes in stratospheric ozone concentrations at Palmer Station. These data demonstrate the usefulness of these assays for environmental photobiology and the potential for their use in studying the relative impacts of UVB versus UVA, including ozone depletion events.     

Phenacenes from Diels-Alder trapping of photogenerated o-xylylenols: phenanthrenes and benzo[e]pyrene bisimide

[structure: see text] The synthesis of phenanthrene and benzo[e]pyrene bisimides, 1 and 2, was accomplished via the Diels-Alder trapping of sterically congested o-xylylenols photochemically generated from 3,6-dibenzoyl-o-xylene and 1,4-dibenzoyl-9,10-dihydroanthracene, respectively. Absorption and emission from 2 are red-shifted from 1 and unsubstituted benzo[e]pyrene. The fluorescence quantum yield for 2 is an order of magnitude lower than that of 1 and comparable to that of the parent benzo[e]pyrene.     

Tricuspid Chordae Tendineae Mechanics: Insertion Site,Leaflet, and Size-Specific Analysis and Constitutive Modelling

Background: Tricuspid valve chordae tendineae play a vital role in our cardiovascular system. They function as “parachute cords” to the tricuspid leaflets to prevent prolapse during systole. However, in contrast to the tricuspid annulus and leaflets, the tricuspid chordae tendineae have received little attention. Few previous studies have described their mechanics and their structure-function relationship. Objective: In this study, we aimed to quantify the mechanics of tricuspid chordae tendineae based on their leaflet of origin, insertion site, and size. Methods: Specifically, we uniaxially stretched 53 tricuspid chordae tendineae from sheep and recorded their stress-strain behavior. We also analyzed the microstructure of the tricuspid chordae tendineae based on two-photon microscopy and histology. Finally, we compared eight different hyperelastic constitutive models and their ability to fit our data. Results: We found that tricuspid chordae tendineae are highly organized collageneous tissues, which are populated with cells throughout their thickness. In uniaxial stretching, this microstructure causes the classic J-shaped nonlinear stress-strain response known from other collageneous tissues. We found differences in stiffness between tricuspid chordae tendineae from the anterior, posterior, or septal leaflets only at small strains. Similarly, we found significant differences based on their insertion site or size also only at small strains. Of the models we fit to our data, we recommend the Ogden two-parameter model. This model fit the data excellently and required a minimal number of parameters. For future use, we identified and reported the Ogden material parameters for an average data set. Conclusion: The data presented in this study help to explain the mechanics and structure-function relationship of tricuspid chordae tendineae and provide a model recommendation (with parameters) for use in computational simulations of the tricuspid valve.

     

Processing studies and thermal stability of addition polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and Bis-dienes

1,4,5,8-Tetrahydro-1,4;5,8-diepoxyanthracene reacts with various anthracene end-capped polymide oligomers to form Diels-Alder cycloaddition copolymers. The polymers are soluble in common organic solvents, and dehydrate thermally at temperatures of 300–350°C to give thermal oxidatively stable pentiptycene units along the polymer backbone. Because of their high softening points and good thermal oxidative stability, the polymers are candidates for matrix resins for high temperature composite applications. To assess their usefulness for such applications, several parameters have been studied affecting the properties of the final polymer. These parameters include varying the formulated molecular weight of the end-capped prepolymers, and use of meta-substituted aromatic diamine in place of some of the para-substituted diamine. Processability of the resins was studied using rheometric spectrometry, and a processing scheme was devised. Finally, several formulations of neat resins were compression molded into coupons, and evaluated for longterm stability in air at 315 and 371°C. The best combination of good processability and thermal oxidative stability was obtained from polymers synthesized with small amounts of meta-diamine substitution and higher formulated molecular weight prepolymers.     

Processable,high temperature polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and bis-dienes

1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene reacts with various anthracene end-capped polyimide oligomers to form Diels–Alder cycloaddition copolymers. The polymers are soluble in common organic solvents, and have molecular weights of approximately 21000 to 32000. Interestingly, these resins exhibit lower weight loss in air than in nitrogen. This is suggested to be due to dehydration (loss of water ranges from 2 to 5%) at temperatures of 390 to 400°C to give thermooxidatively stable pentiptycene units along the polymer backbone. Because of their high softening points and good thermooxidative stability, the polymers have potential as processable, matrix resins for high temperature composite applications.     

Induction, distribution and repair of UV photodamage in the platyfish, Xiphophorus signum

The genus Xiphophorus is an important model for investigating the etiology and genetics of sunlight-induced melanoma as well as other cancers. We used immunological techniques to determine the induction, distribution and repair of cyclobutane pyrimidine dimers (CPD) and pyrimidine(6-4)pyrimidone dimers ([6-4]PD) in different tissues of Xiphophorus signum exposed to ultraviolet-B light. We found that the (6-4)PD was induced at 5 to 10-fold lower frequency than the CPD and that scalation provided considerable photoprotection against both photoproducts. Photoenzymatic repair (PER) was very efficient in X. signum with most of the lesions removed within 20 min; PER of CPD occurred at about twice the rate of (6-4)PD. Nucleotide excision repair (NER) was much less efficient than PER and the rates of CPD and (6-4)PD removal were comparable. PER was more efficient in the caudal fin compared to the lateral epidermis; the opposite was true for NER. Although the initial rate of CPD excision was five-fold faster in the lateral epidermis compared to the caudal fin a considerable amount of residual damage remained in both tissues. The diverse photochemical and photobiological responses observed in X. signum suggest that heritable traits governing deoxyribonucleic acid damage induction and repair may be involved in the susceptibility of other Xiphophorus species to melanomagenesis.     

Wrapping of single-walled carbon nanotubes by a pi-conjugated polymer: the role of polymer conformation-controlled size selectivity

Wrapping of a single-walled carbon nanotube (SWNT) was examined by using a poly[( m-phenylenevinylene)- alt-( p-phenylenevinylene)] (PmPV) derivative. The polymer's intrinsic ability in forming a helical conformation was found to play an essential role in the separation of nanotubes. Among about 15 tubes present in the pure SWNT (HiPcoTM) sample, the polymer was found to selectively pick up the tubes (11,6), (11,7) and (12,6), which correspond to tube diameters of 1.19, 1.25 and 1.24 nm, respectively. The SWNTs of smaller diameters were held loosely by the PmPV, and were gradually dropped out under centrifugation. The suspension solution prepared from the SWNT and PmPV was not permanently stable, with precipitation occurring after a few weeks. Irradiation in the UV-vis region exhibited a catalytic effect to shorten the precipitation time to hours. Those tubes, which were held loosely by PmPV, were quickly separated from the suspension during the irradiation process.