Polymeric Encapsulation of Novel Homoleptic Bis(dipyrrinato) Zinc(II) Complexes with Long Lifetimes for Applications as Photodynamic Therapy Photosensitisers

The use of photodynamic therapy (PDT) to treat cancer has received increasing attention over the last years. However, the clinically used photosensitisers (PSs) have some limitations that include poor aqueous solubility, hepatotoxicity, photobleaching, aggregation, and slow clearance from the body, so the design of new classes of PSs is of great interest. We present the use of bis(dipyrrinato)zinc(II) complexes with exceptionally long lifetimes as efficient PDT PSs. Based on the heavy‐atom effect, intersystem crossing of these complexes changes the excited state from singlet to a triplet state, thereby enabling singlet oxygen generation. To overcome the limitation of quenching effects in water and improve water solubility, the lead compound 3 was encapsulated in a polymer matrix. It showed impressive phototoxicity upon irradiation at 500 nm in various monolayer cancer cells as well as 3D multicellular tumour spheroids, without observed dark toxicity.     

Method for detecting and characterising actinide-bearing micro-particles in soils and sediment of the Fukushima Prefecture,Japan

An aqueous biphasic system has been used for selective extraction of U(VI) ions from Th(IV), Sm(III) and Ce(III). Role of different biomolecules like morin, catechin, hesperidin and 4-hydroxycoumarin have been studied. Morin serves as the best reagent when citrate ions are used as a masking agent. Citrate forms stronger complexes with the other metal ions than morin thereby restricting their extractions. Contrarily, U(VI) forms a stronger complex with morin than citrate and is selectively extracted under the same conditions. It was also observed that morin can act as a spectrophotometric reagent for ratiometric detection and analysis of U(VI) ions.

     

Detailed experimental and kinetic modeling study of 3-carene pyrolysis

3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

pH-Dependent Hydration Change in a Gd-Based MRI Contrast Agent with a Phosphonated Ligand

The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by ¹⁷O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm ⁻¹⋅s⁻¹ (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by ¹H and ³¹P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations.     

Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.