The Synthesis and Characterization of New, Robust Titanium (IV) Scorpionate Complexes

Titanium complexes possessing sterically encumbered ligands have allowed for the preparation of reactive moieties (imido, alkylidene and alkylidyne species) relevant to reactions such as olefin polymerization and alkyne hydroamination. For this reason, we have targeted robust scorpionate ancillary ligands to support reactive titanium centers. Thus, a series of titanium complexes were synthesized using an achiral oxazoline-based scorpionate ligand, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate [To^M^]^-^ as well as the related chiral ligand, tris(4-isopropyl-2-oxazolinyl)phenyl borate [To^P^]^-^. The complex [Ti(κ^3^- To^M^)Cl~3~] was prepared in moderate yield (43%) by the rapid (<1 min at room temperature) reaction of Li[To^M^] and TiCl~4~ in methylene chloride; this new compound was characterized by ^1^H NMR spectroscopy as the expected C~3v~-symmetric species. One route to Ti (IV) alkyls involves salt metathesis; accordingly, syntheses of [To^M^]Ti alkyl complexes by interaction of [Ti(κ^3^-To^M^)Cl~3~] and one or three equivalents of alkylating agents, such as benzyl potassium (KCH~2~C~6~H~5~), trimethylsilylmethyl
lithium (LiCH~2~Si(CH~3~) ~3~), or neopentyl lithium (LiCH~2~C(CH~3~)~3~) are currently under investigation. The complexes [Ti(=NBut) (κ~3~-To^M^)(Cl)(Bu^t^py)] (Bu^t^py=4 tert-butylpyridine) and [Ti(=NBu^t^) (κ~3~-To^P^)(Cl)(Bu^t^py)] were synthesized by reaction of the known Ti imido [Ti(=NBu^t^)(Cl)~2~(Bu^t^py)~2~] with Li[To^M^] or Li[To^P^], respectively, by stirring overnight in methylene chloride at ambient temperature. The complexes were identified using ^1^H NMR spectroscopy, ^1^H-^13^C HMQC and ^1^H-^15^N HMBC correlation experiments

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ISM Properties in Low-Metallicity Environments II. The Dust Spectral Energy Distribution of NGC 1569

We present new 450 and 850 microns SCUBA data of the dwarf galaxy NGC 1569. We construct the mid-infrared to millimeter SED of NGC 1569, using ISOCAM, ISOPHOT, IRAS, KAO, SCUBA and MAMBO data, and model the SED in order to explore the nature of the dust in low metallicity environments. The detailed modeling is performed in a self-consistent way, synthesizing the global ISRF of the galaxy using an evolutionary synthesis model with further constraints provided by the observed MIR ionic lines and a photoionisation model. Our results show that the dust properties are different in this low metallicity galaxy compared to other more metal rich galaxies. The results indicate a paucity of PAHs probably due to the destructive effects of the ISRF penetrating a clumpy environment and a size-segregation of grains where the emission is dominated by small grains of size ~3 nm, consistent with the idea of shocks having a dramatic effect on the dust properties in NGC 1569. A significant millimetre excess is present in the dust SED which can be explained by the presence of ubiquitous very cold dust (T = 5-7 K). This dust component accounts for 40 to 70 % of the total dust mass in the galaxy (1.6 - 3.4 10^5 Msol) and could be distributed in small clumps (size a few pc) throughout the galaxy. We find a gas-to-dust mass ratio of 740 - 1600, larger than that of the Galaxy and a dust-to-metals ratio of 1/4 to 1/7. We generate an extinction curve for NGC 1569, consistent with the modeled dust size distribution. This extinction curve has relatively steep FUV rise and smaller 2175 Angstroms bump, resembling the observed extinction curve of some regions in the Large Magellanic Cloud.Comment: 20 pages, 20 figures, accepted by A&

Mapping the cold dust temperatures and masses of nearby Kingfish galaxies with Herschel

Taking advantage of the sensitivity and angular resolution of the Herschel Space Observatory at far-infrared and submm wavelengths, we aim to characterize the physical properties of cold dust within nearby galaxies and study the robustness of the parameters we derive using different modified blackbody models. For a pilot subsample of the KINGFISH program, we perform 2 temperature fits of the Spitzer and Herschel photometric data (24 to 500um), with a warm and a cold component, globally and in each resolution element.At global scales, we observe ranges of values for beta_c(0.8 to 2.5) and Tc(19.1 to 25.1K).We compute maps of our parameters with beta fixed or free to test the robustness of the temperature and dust surface density maps we deduce. When the emissivity is fixed, we observe temperature gradients as a function of radius.When the emissivity is fitted as a free parameter, barred galaxies tend to have uniform fitted emissivities.Gathering resolved elements in a Tc-beta_c diagram underlines an anti-correlation between the two parameters.It remains difficult to assess whether the dominant effect is the physics of dust grains, noise, or mixing along the line of sight and in the beam. We finally observe in both cases that the dust column density peaks in central regions of galaxies and bar ends (coinciding with molecular gas density enhancements usually found in these locations).We also quantify how the total dust mass varies with our assumptions about the emissivity index as well as the influence of the wavelength coverage used in the fits. We show that modified blackbody fits using a shallow emissivity (beta_c < 2.0) lead to significantly lower dust masses compared to the beta_c < 2.0 case, with dust masses lower by up to 50% if beta_c=1.5 for instance.The working resolution affects our total dust mass estimates: masses increase from global fits to spatially-resolved fits.Comment: 26 pages, 12 figures, 4 tables, accepted for publication in MNRAS, 2012 June 2

Synthesis and characterisation of a nucleotide based pro-drug formulated with a peptide into a nano-chemotherapy for colorectal cancer

Recent studies in colorectal cancer patients (CRC) have shown that increased resistance to thymidylate synthase (TS) inhibitors such as 5-fluorouracil (5-FU), reduce the efficacy of standard of care (SoC) treatment regimens. The nucleotide pool cleanser dUTPase is highly expressed in CRC and is an attractive target for potentiating anticancer activity of chemotherapy. The purpose of the current work was to investigate the activity of P1, P4-di(2',5'-dideoxy-5'-selenouridinyl)-tetraphosphate (P4-SedU2), a selenium-modified symmetrically capped dinucleoside with prodrug capabilities that is specifically activated by dUTPase. Using mechanochemistry, P4-SedU2 and the corresponding selenothymidine analogue P4-SeT2 were prepared with a yield of 19% and 30% respectively. The phosphate functionality facilitated complexation with the amphipathic cell-penetrating peptide RALA to produce nanoparticles (NPs). These NPs were designed to deliver P4-SedU2 intracellularly and thereby maximise in vivo activity. The NPs demonstrated effective anti-cancer activity and selectivity in the HCT116 CRC cell line, a cell line that overexpresses dUTPase; compared to HT29 CRC cells and NCTC-929 fibroblast cells which have reduced levels of dUTPase expression. In vivo studies in BALB/c SCID mice revealed no significant toxicity with respect to weight or organ histology. Pharmacokinetic analysis of blood serum showed that RALA facilitates effective delivery and rapid internalisation into surrounding tissues with NPs eliciting lower plasma Cmax than the equivalent injection of free P4-SedU2, translating the in vitro findings. Tumour growth delay studies have demonstrated significant inhibition of growth dynamics with the tumour doubling time extended by &gt;2weeks. These studies demonstrate the functionality and action of a new pro-drug nucleotide for CRC. </p

A surprising consistency between the far-infrared galaxy luminosity functions of the field and Coma

We present new deep images of the Coma Cluster from the ESA Herschel Space Observatory at wavelengths of 70, 100 and 160 mu m, covering an area of 1.75 x 1.0 square degrees encompassing the core and south-west infall region. Our data display an excess of sources at flux densities above 100 mJy compared to blank-field surveys, as expected. We use extensive optical spectroscopy of this region to identify cluster members and hence produce cluster luminosity functions in all three photometric bands. We compare our results to the local field galaxy luminosity function, and the luminosity functions from the Herschel Virgo Cluster Survey. We find consistency between the shapes of the Coma and field galaxy luminosity functions at all three wavelengths; however, we do not find the same level of agreement with that of the Virgo Cluster.</p

Probing the Dust Properties of Galaxies at Submillimetre Wavelengths II. Dust-to-gas mass ratio trends with metallicity and the submm excess in dwarf galaxies

We are studying the effects of submm observations on the total dust mass and thus dust-to-gas mass ratio measurements. We gather a wide sample of galaxies that have been observed at submm wavelengths to model their Spectral Energy Distributions using submm observations and then without submm observational constraints in order to quantify the error on the dust mass when submm data are not available. Our model does not make strong assumptions on the dust temperature distribution to precisely avoid submm biaises in the study. Our sample includes 52 galaxies observed at submm wavelengths. Out of these, 9 galaxies show an excess in submm which is not accounted for in our fiducial model, most of these galaxies being low- metallicity dwarfs. We chose to add an independant very cold dust component (T=10K) to account for this excess. We find that metal-rich galaxies modelled with submm data often show lower dust masses than when modelled without submm data. Indeed, these galaxies usually have dust SEDs that peaks at longer wavelengths and require constraints above 160 um to correctly position the peak and sample the submillimeter slope of their SEDs and thus correctly cover the dust temperature distribution. On the other hand, some metal-poor dwarf galaxies modelled with submm data show higher dust masses than when modelled without submm data. Using submm constraints for the dust mass estimates, we find a tightened correlation of the dust-to-gas mass ratio with the metallicity of the galaxies. We also often find that when there is a submm excess present, it occurs preferentially in low-metallicity galaxies. We analyse the conditions for the presence of this excess and find a relation between the 160/850 um ratio and the submm excess.Comment: 19 pages, 10 figures, 1 table, accepted for publication in A&