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        Lanthanide luminescence efficiency in eight- and nine-coordinate complexes: Role of the radiative lifetime

        Bunzli, J.C.G.,Chauvin, A.S.,Kim, H.K.,Deiters, E.,Eliseeva, S.V. Elsevier Publishing Company 2010 Coordination Chemistry Reviews Vol. No.

        The photophysical parameters for the sensitization of metal-centred luminescence are analyzed in two series of complexes with tridentate and hexadentate ligands having N<SUB>x</SUB>O<SUB>y</SUB> chelating units. In particular, the radiative lifetime τ<SUB>rad</SUB> is experimentally estimated for 29 nine-coordinate Eu<SUP>III</SUP> complexes and 10 eight- and nine-coordinate Yb<SUP>III</SUP> complexes. The known dependence of τ<SUB>rad</SUB> on refractive index is substantiated by comparing data for solid-state samples and solutions. Moreover, a clear dependence of τ<SUB>rad</SUB> with the coordination environment is evidenced and in the case of Eu<SUP>III</SUP>, a comparison between τ<SUB>rad</SUB> and the nephelauxetic effect generated by the ligands is attempted. Altogether, this extensive analysis points to the importance of having a handle on τ<SUB>rad</SUB> when designing ligands for highly luminescent lanthanide-containing molecular edifices. This, in turn, should stimulate initiating theoretical considerations to unravel a reliable relationship between τ<SUB>rad</SUB> and the electronic structure of the ligands.

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        Bioconjugated lanthanide luminescent helicates as multilabels for lab-on-a-chip detection of cancer biomarkers

        Ferná,ndez-Moreira, Vanesa,Song, Bo,Sivagnanam, Venkataragavalu,Chauvin, Anne-Sophie,Vandevyver, Caroline D. B.,Gijs, Martin,Hemmilä,, Ilkka,Lehr, Hans-Anton,,nzli, Jean-Claude G. Royal Society of Chemistry 2010 The Analyst Vol.135 No.1

        <P>The lanthanide binuclear helicate [Eu<SUB>2</SUB>(L<SUP>C2(CO<SUB>2</SUB>H)</SUP>)<SUB>3</SUB>] is coupled to avidin to yield a luminescent bioconjugate <B>EuB1</B> (<I>Q</I> = 9.3%, <I>τ</I>(<SUP>5</SUP>D<SUB>0</SUB>) = 2.17 ms). MALDI/TOF mass spectrometry confirms the covalent binding of the Eu chelate and UV-visible spectroscopy allows one to determine a luminophore/protein ratio equal to 3.2. Bio-affinity assays involving the recognition of a mucin-like protein expressed on human breast cancer MCF-7 cells by a biotinylated monoclonal antibody 5D10 to which <B>EuB1</B> is attached <I>via</I> avidin-biotin coupling demonstrate that (i) avidin activity is little affected by the coupling reaction and (ii) detection limits obtained by time-resolved (TR) luminescence with <B>EuB1</B> and a commercial Eu-avidin conjugate are one order of magnitude lower than those of an organic conjugate (FITC-streptavidin). In the second part of the paper, conditions for growing MCF-7 cells in 100–200 µm wide microchannels engraved in PDMS are established; we demonstrate that <B>EuB1</B> can be applied as effectively on this lab-on-a-chip device for the detection of tumour-associated antigens as on MCF-7 cells grown in normal culture vials. In order to exploit the versatility of the ligand used for self-assembling [Ln<SUB>2</SUB>(L<SUP>C2(CO<SUB>2</SUB>H)</SUP>)<SUB>3</SUB>] helicates, which sensitizes the luminescence of both Eu<SUP><SMALL>III</SMALL></SUP> and Tb<SUP><SMALL>III</SMALL></SUP> ions, a dual on-chip assay is proposed in which estrogen receptors (ERs) and human epidermal growth factor receptors (Her2/<I>neu</I>) can be simultaneously detected on human breast cancer tissue sections. The Ln helicates are coupled to two secondary antibodies: ERs are visualized by red-emitting <B>EuB4</B> using goat anti-mouse IgG and Her2/<I>neu</I> receptors by green-emitting <B>TbB5</B> using goat anti-rabbit IgG. The fact that the assay is more than 6 times faster and requires 5 times less reactants than conventional immunohistochemical assays provides essential advantages over conventional immunohistochemistry for future clinical biomarker detection.</P> <P>Graphic Abstract</P><P>Lanthanide luminescent bioprobes (LLBs) combined with microfluidics and lab-on-a-chip technology lead to fast dual assays of cancerous tissue biomarkers. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b922124g'> </P>

      • Does Healthy Food Access Matter in a French Urban Setting?

        Caillavet, France,Kyureghian, Gayaneh,Nayga Jr., Rodolfo M.,Ferrant, Coline,Chauvin, Pierre Oxford University Press 2015 AMERICAN JOURNAL OF AGRICULTURAL ECONOMICS - Vol.97 No.5

        <P>Limited access to healthy food is commonly regarded as a contributing factor to poor dietary choices. The objective of this article is to test this hypothesis in a French context given France's increasing obesity rates and incidence of poor dietary habits. We use data on fruit and vegetable consumption frequency and different food retail availability measures, for example the number of food stores, food surface area, and a dispersion measure based on store numbers, store types, and food area surface, from several data sources in France. We also employ different types of geographic units when measuring the food retail environment and instrumental variable model specifications to test the robustness of our results, which indicate that fewer but larger retail outlets increase the odds of consuming the recommended level of fruit and vegetables. We also find that an increase in food supply dispersion will improve fruit and vegetable consumption in Paris, but not in its suburbs.</P>

      • Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

        Baek, Nam Seob,Kim, Yong Hee,Eom, Yu Kyung,Oh, Jung Hwan,Kim, Hwan Kyu,Aebischer, Annina,Gumy, Fré,,ric,Chauvin, Anne-Sophie,,nzli, Jean-Claude G. Royal Society of Chemistry 2010 Dalton Transactions Vol.39 No.6

        <P>Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. The ligand substituents consist of a carbazole moiety with hole-transport properties and an aromatic or heteroaromatic unit. According to quantitative NMR analysis and complementary HPLC experiments, the diketones are predominantly in their enolic form in polar solvents such as THF and MeCN at room temperature. The preferred <I>cis</I>-enol form contributes strongly to the binding of lanthanide ions (Ln = Nd, Gd, Er). The resulting tris(diketonate) ternary complexes with terpyridine (Ln = Nd, Er) display sizeable near-IR emission with long luminescence lifetimes.</P> <P>Graphic Abstract</P><P>Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=b915893f'> </P>

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