Water-soluble sapphyrins

Sapphyrins are provided having appended functional groups that render the sapphyrin water-soluble. Such water-soluble sapphyrins are useful for photodynamic therapy, for example.Board of Regents, University of Texas Syste

Sapphyrin multimers

The present invention provides novel sapphyrin dimers, trimers, oligomers and polymers, which multimers may include repeating units of sapphyrin or sapphyrin derivatives alone, or may further incorporate other units such as nucleobases.Board of Regents, University of Texas Syste

A self-consistent model for the evolution of the gas produced in the debris disc of β Pictoris

This paper presents a self-consistent model for the evolution of gas produced in the debris disc of β Pictoris. Our model proposes that atomic carbon and oxygen are created from the photodissociation of CO, which is itself released from volatile-rich bodies in the debris disc due to grain–grain collisions or photodesorption. While the CO lasts less than one orbit, the atomic gas evolves by viscous spreading resulting in an accretion disc inside the parent belt and a decretion disc outside. The temperature, ionization fraction and population levels of carbon and oxygen are followed with the photodissociation region model CLOUDY, which is coupled to a dynamical viscous α model. We present new gas observations of β Pic, of C I observed with Atacama Pathfinder EXperiment and O I observed with $\textit{Herschel}$, and show that these along with published CII and CO observations can all be explained with this new model. Our model requires a viscosity α > 0.1, similar to that found in sufficiently ionized discs of other astronomical objects; we propose that the magnetorotational instability is at play in this highly ionized and dilute medium. This new model can be tested from its predictions for high-resolution ALMA observations of C I. We also constrain the water content of the planetesimals in β Pic. The scenario proposed here might be at play in all debris discs and this model could be used more generally on all discs with C, O or CO detections.QK, MW and LM acknowledge support from the European Union through ERC grant number 279973. AJ acknowledges the support of the DISCSIM project, grant agreement 341137, funded by the European Research Council under ERC-2013-ADG.This is the final version of the article. It first appeared from Oxford University Press via http://dx.doi.org/10.1093/mnras/stw136

Landscape Genomics and Climatic Responses of Willamette Valley Alders

The climate of the Pacific Northwest is in flux, and existing forest ecosystems are stressed and poised to shift in fundamental ways, with or without human intervention. This dissertation probes the nature of forest responses to environmental change through investigations of morphology and genetics of three species of alder co-occurring in the Willamette Valley, Oregon. Chapter 1 provides an introduction to the genus Alnus and reviews some ways in which hybridization among species, including alders, may be relevant to forest responses to changing environments. Chapter 2 describes geographic and taxonomic patterns of relationships in the plastid-based phylogeny of 114 western alders, mostly from the Willamette Valley. Through genome skimming and whole-plastome analysis, we discovered that alders in our sampling tend to share plastids with neighboring trees irrespective of taxonomy. We found that the Willamette Valley is dominated by a single plastid lineage which is subdivided into geographically localized sub-lineages distinguished by just one or two SNP’s or indels. Some of the geographically-structured clades separate populations only 10 km distant, providing evidence of recent interspecific hybridization within the Willamette Valley, and suggesting that recent seed migration, particularly among white alder populations, is highly constrained except along the Willamette River. In Chapter 3, we built upon the findings of chapter 2 by adding analyses of differences in seed dispersibility and plastid diversity between red and white alder. In a wind-tunnel seed dispersal experiment, we found that red alder seed is the better disperser, which is supported in the general distribution of red alder plastid diversity within the Willamette Valley. White alder plastid populations, on the other hand, tend to be isolated from one another and more related to nearby red alders, suggesting a possibly dominant role of pollen-mediated migration in this species. We test this hypothesis with a simple model relating within-stand diversity to stand composition. We also attempt to differentiate pollen-mediated migration from seed-mediated migration by comparing plastid diversity in stands along mainstem rivers with diversity in tributary watersheds. Chapter 4 presents two comparative analyses of red and white alder within the Willamette Valley. Based on 19 distinguishing characters in 92 red, white, and putative hybrid alders, a morphological analysis arrayed field identifications against a morphological index. We found indications of hybridity not only in field-identified putative hybrids, but also in many putative red and white alder, suggesting widespread admixture within these populations. The occurrence of admixture was further supported by the inclusion of F1 progeny of known red and white alder parentage in hybrid analyses. A wood mass-spectrometry analysis designed to distinguish species and hybrids instead uncovered a high degree of metabolomic similarity, particularly between red and white alder, a finding consistent with introgression and admixture of the taxa. In Chapter 5, we present an initial analysis of three years of data collected from an array of four common gardens spanning an environmental gradient, from the floor of the Willamette Valley to the crest of the Oregon Coast Range. Each garden was planted with over 1000 progeny of known parentage of red, white and putative hybrid alders from 12 stands across the Willamette Valley. We analyzed survival and growth of progeny and examined responses along temperature and precipitation clines. We found striking differences in survival between species, with white alder out-surviving red alder in every garden, even in the Oregon Coast Range, well beyond white alder’s current limits. Red alder was the fastest growing in every comparison, and hybrids were intermediate, but growth of red alder was severely curtailed by mortality in valley-floor gardens. These findings are consistent with those of Chapter 6, which suggest a northward contraction of the range of red alder. Chapter 6 is a broad analysis of the changing climate and forest of the Willamette Valley. The current health of eight tree species, four with ranges extending northward from the Willamette Valley and four southward, are compared through an assessment of 792 individual trees from stands throughout the northern and central valley. We found that all four northward-ranging species, including red alder, were faring poorly relative to southward-ranging species, with elevated rates of severe crown decline and mortality. Southward-ranging species, by contrast, including white alder, were comparatively healthy. These findings suggest ongoing decline of temperate forest species as temperatures rise and summer precipitation decreases

Hydroxylated texaphyrins

A method of using texaphyrins as radiosensitizers. Advantageous properties of texaphyrins for use as a radiosensitizer include i) a low redox potential which allows radiation induced solvated electrons to flow to texaphyrin rather than neutralizing hydroxyl radicals, allowing the hydroxyl radicals to cause cellular damage, ii) a relatively stable texaphyrin radical which, nevertheless, reacts readily to covalently modify neighboring molecules causing further cellular damage, and iii) intrinsic biolocalization and indifference to the presence of O.sub.2 which allow texaphyrin to be particularly effective for treating the hypoxic areas of solid tumors. Sensitizer enhancement ratios of 1.62 and 2.2 were achieved at 20 .mu.M and 80 .mu.M gadolinium-texaphyrin, respectively, with a mouse leukemia cell line. Methods of treatment for an individual having a tumor include the use of a texaphyrin as a radiosensitizer and as an agent for photodynamic tumor therapy, or the use of a texaphyrin for internal and for external ionizing radiation. New water soluble hydroxy-substituted texaphyrins are described.Board of Regents, University of Texas Syste

Method of cleaving DNA

The present invention provides various novel covalently modified sapphyrin derivatives and conjugates; polymers including sapphyrin or derivatives thereof; and chromatographic supports including sapphyrins and other expanded porphyrins and derivatives thereof. Disclosed are water soluble sapphyrins, including polyhydroxysapphyrins and sapphyrin-sugar derivatives; sapphyrin-metal chelating conjugates; sapphyrin nucleobase conjugates; oligosapphyrins and polysapphyrins, including sapphyrin dimers, trimers, oligomers and higher polymers; and polymer supported expanded porphyrin compositions, including advantageous rubyrin- and sapphyrin-based chromatography columns and electrophoretic supports. Sapphyrin oligomers and polymers and polymer supported expanded porphyrins, such as, e.g., glass and silica expanded porphyrin constructs, are disclosed which include both repeating units of sapphyrin derivatives alone and which include other units, for example, nucleobases, sapphyrin-nucleobase conjugates and long chain alkyl groups.Board of Regents, University of Texas Syste

Method for separating molecules

The present invention provides various novel covalently modified sapphyrin derivatives and conjugates; polymers including sapphyrin or derivatives thereof; and chromatographic supports including sapphyrins and other expanded porphyrins and derivatives thereof. Disclosed are water soluble sapphyrins, including polyhydroxysapphyrins and sapphyrin-sugar derivatives; sapphyrin-metal chelating conjugates; sapphyrin nucleobase conjugates; oligosapphyrins and polysapphyrins, including sapphyrin dimers, trimers, oligomers and higher polymers; and polymer supported expanded porphyrin compositions, including advantageous rubyrin- and sapphyrin-based chromatography columns and electrophoretic supports. Sapphyrin oligomers and polymers and polymer supported expanded porphyrins, such as, e.g., glass and silica expanded porphyrin constructs, are disclosed which include both repeating units of sapphyrin derivatives alone and which include other units, for example, nucleobases, sapphyrin-nucleobase conjugates and long chain alkyl groups.Board of Regents, University of Texas Syste

Texaphyrin solid supports and devices

The present invention provides various novel matrix-supported texaphyrins in which a polymeric or solid matrix is covalently modified by the addition of one or more texaphyrins or texaphyrin derivatives. Described are methods of making various polymer-supported texaphyrins, including texaphyrin chromatographic supports, and devices such as catheters, as may be used, for example, in the separation of neutral and anionic species and in applications concerning phosphate ester hydrolysis, other catalytic schemes, MRI, and PDT.Board of Regents, University of Texas Syste

Method of magnetic resonance image enhancement

Texaphyrins are provided for use as radiation sensitizers. Advantageous properties of texaphyrins for use as a radiation sensitizer include: i) a low redox potential which allows radiation-induced hydrated electrons to flow to texaphyrin rather than neutralizing hydroxyl radicals, allowing hydroxyl radicals to cause cellular damage, ii) a relatively stable texaphyrin radical that reacts readily to covalently modify neighboring molecules causing further cellular damage, iii) intrinsic biolocalization, and iv) indifference to the presence or absence of O.sub.2. These properties allow texaphyrins to be particularly effective for treating the hypoxic areas of solid neoplasms. Methods of treatment for an individual having a neoplasm or atheroma include the use of a texaphyrin as a radiation sensitizer and as an agent for photodynamic tumor therapy, or the use of a texaphyrin for internal and for external ionizing radiation. Novel texaphyrins are provided.Board of Regents, University of Texas Syste