Terthienyl-Based Redox-Switchable Hemilabile Ligands: Transition Metal Polymeric Complexes with Electrochemically Tunable or Switchable Coordination Environments?

By controlling the extent of oxidation of the polymeric forms of the new class of isolable, polymerizable terthienyl Ru^II complexes 1 , one can modulate both the binding strength of the polymer backbone for Ru^II and the electronic nature of the bound metal centers.     

The First One‐Pot Synthesis of Metal–Organic Frameworks Functionalised with Two Transition‐Metal Complexes

The synthesis of a metal–organic framework (UiO‐67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one‐pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X‐ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO‐67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl]^2?; bpydc=2,2′‐bipyridine‐5,5′‐dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre‐functionalisation methodology.     

Simplex optimization of the separation of phospholipids by high-pressure liquid chromatography

A simplex procedure is shown to be an efficient approach for solving separation problems. The best solvent ratio for the separation of phosphatidylcholine and sphingomyelin has been found by means of a two-dimensional simplex capable of expansion and contraction. A successful high-pressure liquid chromatography separation of lysophosphatidylcholine, phoaphatidylethanolamine, phosphatidylinositol, phosphatidylserine, phosphatidylcholine, sphingomyelin and phosphatidic acid was achieved with a 180-cm column packed with Corasil II and a solvent mixture of chloroform—methanol—ammonia (50.0:35.9:7.0, v/v/v).     

PHOTOCHEMICAL PROPERTIES OF PORPHYRIN c: AN AGENT FOR USE IN TUMOR PHOTOTHERAPY

Abstract— The absorption and fluorescence properties of porphyrin c (P c ), the porphyrin chromophore present in cytochrome c , have been determined in several solvents and micellar environments. In aqueous buffer solutions at pH 7.5 Pc may exist in both a fluorescent monomeric form with quantum yield of fluorescence, (Φ_f,) ∼ 0.03, and fluorescence lifetime, (τ_f) ∼ 8 ns, and as a non-fluorescent aggregate. The proportion of monomeric form is higher in organic solvents and micelles but is reduced with increasing porphyrin concentrations in aqueous solutions. Porphyrin c readily complexes with Zn²⁺ to produce a fluorescent chelate (Zn-P c ) with Φ_f, ∼ 0.02 and τ_f, ∼ 2 ns at pH 7.5. The yields of singlet excited oxygen formation from Pc and the Zn-P c complex are higher than observed for hematoporphyrin derivative (HpD). Both P c and Zn-P c are effective agents in tumor phototherapy and do not induce the prolonged cutaneous photosensitivity observed with the use of HpD.     

Ultraviolet Radiation in the Rhône River Lenses of Low Salinity and in Marine Waters of the Northwestern Mediterranean Sea: Attenuation and Effects on Bacterial Activities and Net Community Production

The high content in nutrients of freshwater outflows induces highly productive and buoyant plumes spreading over marine waters (MW). As a consequence, the growth of organisms developing in these low‐salinity waters (LSW) might be potentially affected by UV‐R (280–400 nm). This study investigated the penetration of UV‐R and its impact on net community production (NCP) and bacterial protein (B_PROTS) and DNA (B_DNAS) synthesis in mesotrophic‐LSW formed from the Rhône River and in oligotrophic MW of the Northwestern Mediterranean Sea (Gulf of Lions) in May 2006. High concentrations of chlorophyll a (up to 8 μg L^?1) measured in the LSW (<37.8 psu, 0–10 m) were the main factor influencing the diffuse attenuation coefficients (K_d) of both UV‐R and photosynthetically active radiation (PAR). The mean ratio of the K_d measured between the LSW and the MW increased with wavelength from 2.4 at 305 nm to 2.9 at 380 nm and 3.1 for PAR indicating more similarity in the UV region. NCP was severely inhibited by UV‐R at the surface of the LSW, whereas no effect was measured in the surrounding MW. In contrast, B_PROTS and B_DNAS were affected deeper by UV‐R in the MW (up to 8 m depth) compared to the LSW where inhibition was only observed at the surface. Differences in response of bacteria in LSW and MW are largely explained by differences in UV‐R transparency; however, transplant experiments indicate that bacterial assemblages from the MW were also more sensitive to UV‐R than those present in the LSW. We also observed that higher activity of bacteria after nutrient additions increased their sensitivity to UV‐R during the day, but favored their recovery during the night incubation period for both LSW and MW. Results suggest that riverine and nutrient inputs may alter the effects of UV‐R on microbial activity by attenuating the UV‐R penetration and by modifying the physiology of bacteria.     

Exceptional near-infrared fluorescence quantum yields and excited-state absorptivity of highly conjugated porphyrin arrays

We show that meso-to-meso ethyne-bridged (porphinato)zinc(II) oligomers (PZnn structures) define exceptional low band gap organic materials that possess both large magnitude NIR S1 --> S0 fluorescence quantum yields and substantial S1 --> Sn absorptive cross-sections, tunable over a wide 850-1400 nm spectral window. These PZnn species possess fluorescence quantum yields (phif values) comparable to the highest reported for NIR laser dyes in the 750-900 nm regime; importantly, these emitters do not suffer from commonly cited tricarbocyanine dye drawbacks of poor photostability and substantial phif sensitivity to solvent polarity. Furthermore, tauo (kr-1) values determined using the Strickler-Berg method highlight the close correlation of fluorescence quantum yields with S0 --> S1 integrated oscillator strength and demonstrate a rare if not unique example of broad NIR spectral domain fluorescence energy modulation, where phif magnitudes follow a simple Strickler-Berg relationship.     

A new type of luminescent alkynyl Au4Cu2 cluster

Changes in the optical properties of an alkynyldigold(I) complex upon reaction with Cu(I) are associated with a complicated structural change to form an unusual Au4Cu2 cluster with metallophilic interactions as well as pi-alkyne coordination.     

A STEM/EELS method for mapping iron valence ratios in oxide minerals

The valence state of iron in minerals has useful applications in the geosciences for estimating redox conditions during mineral formation or re-equilibration. STEM/EELS techniques offer the advantage over other methods of being able to measure Fe valence with very high spatial resolution across mineral grains and grain boundaries. We have modified an EELS method for point analyses of iron valence ratios (Fe(3+)/SigmaFe) making it possible to generate line scans and maps of Fe valence. We demonstrate this method with measurements at an interface between iron-bearing oxides in a finely intergrown sample of magnetite and ilmenite. The STEM/EELS method is based on a calibrated relationship between Fe(3+)/SigmaFe and the relative intensities of the Fe L(3) and L(2) white lines in core energy-loss spectra for oxide and silicate minerals. Our method overcomes problems of energy drift in spectrum images by aligning energy-loss edges at a fixed energy position prior to background removal. An automated routine for batch processing of core loss spectra, including additional background removal and calculation of Fe L(3)/L(2) intensity ratios, allows for rapid Fe(3+)/SigmaFe determinations of multiple point analyses or spectrum images and the preparation of Fe valence maps, with an analytical error of +/-0.05 to +/-0.09 in the Fe(3+)/SigmaFe measurements.     

Solid State Structure of 6,7-Dihydro-1,4-Di(2′-Pyridyl)-5<Emphasis Type="Italic">H</Emphasis>-Cyclopenta[d]Pyridazine

Abstract  The X-ray structure of 6,7-dihydro-1,4-di(2′-pyridyl)-5H-cyclopenta[d]pyridazine ligand (5-dppn) shows the existence of a trans/trans conformation. The 5-dppn crystallizes in a triclinic space group P-1 with a = 7.1048(15) ?; b = 9.008(2) ?; c = 10.986(3) ?; α = 88.279(16)°; β = 85.454(15)°; γ = 69.104(12)°; V = 654.7(3) ?³ and Z = 2. The analysis of 5-dppn crystal structure demonstrates the presence of edge-edge Ar–H···N and face-face Aliph-H···N centrosymmetric dimer interactions. The unit cell packing arrangement confirmed the presence of two molecules opposite to each other. Index Abstract  The X-ray structure of 6,7-dihydro-1,4-di(2′-pyridyl)-5H-cyclopenta[d]pyridazine ligand (5-dppn) shows the existence of a trans/trans conformation.