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Lee, Doh-Kwon,Fischer, Claus C.,Valov, Ilia,Reinacher, Jochen,Stork, Alexandra,Lerch, Martin,Janek, Juergen The Royal Society of Chemistry 2011 Physical chemistry chemical physics Vol.13 No.3
<P>The mobility and electrochemical activity of nitrogen inside and/or at the surface of ionic compounds is of fundamental, as well as of possibly practical, relevance. In order to better understand the role of nitrogen anions in solid electrolytes, we measured the transference number of nitrogen in yttria-stabilized zirconia (YSZ) by a concentration cell technique as a function of oxygen activity at different temperatures in the range of 1023 ≤<I>T</I>/<I>K</I>≤ 1123. YSZ doped with 1.9 wt% of N (YSZ:N) turned out to have an appreciable nitrogen transference number, which increased from 0 to 0.1 with decreasing oxygen activity in the range of −20 < log<I>a</I><SUB>O<SUB>2</SUB></SUB> < −14. The stability of N in YSZ:N, however, has yet to be elucidated under oxidizing conditions.</P> <P>Graphic Abstract</P><P>Solid state electrochemistry with (di-)nitrogen? EMF measurements with a zirconium oxide nitride (N-doped YSZ) solid electrolyte under reducing conditions reveal a significant transference number of nitrogen anions. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c003991h'> </P>
Rö,nsberg, David,Debbab, Abdessamad,Má,ndi, Attila,Vasylyeva, Vera,Bö,hler, Philip,Stork, Bjö,rn,Engelke, Laura,Hamacher, Alexandra,Sawadogo, Richard,Diederich, Marc,Wray, Vict American Chemical Society 2013 Journal of organic chemistry Vol.78 No.24
<P>Four tetrahydroxanthone dimers (<B>1</B>–<B>4</B>) and four biogenetically related monomers (<B>5</B>–<B>8</B>), including the new derivatives <B>4</B>–<B>6</B>, were isolated from the endophyte Phomopsis longicolla. The absolute configurations of <B>2</B>–<B>4</B> were established for the first time by TDDFT electronic circular dichroism calculations, and that of phomoxanthone A (<B>1</B>) was revised by X-ray crystallography. Phomoxanthone A (<B>1</B>) showed the strongest pro-apoptotic activity when tested against a panel of human cancer cell lines, including cisplatin-resistant cells, whereas it was up to 100-fold less active against healthy blood cells. It was also the most potent activator of murine T lymphocytes, NK cells, and macrophages, suggesting an activation of the immune system in parallel to its pro-apoptotic activity. This dual effect in combating cancer cells could help in fighting resistance during chemotherapy. Preliminary structure–activity studies of isolated compounds and derivatives obtained by semisynthesis (<B>9a</B>–<B>11</B>) hinted at the location of the biaryl axis and the presence of acetyl groups as important structural elements for the biological activity of the studied tetrahydroxanthones.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/joceah/2013/joceah.2013.78.issue-24/jo402066b/production/images/medium/jo-2013-02066b_0011.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/jo402066b'>ACS Electronic Supporting Info</A></P>
van der Put, Robert M. F.,Kim, Tae Hee,Guerreiro, Catherine,Thouron, Franç,oise,Hoogerhout, Peter,Sansonetti, Philippe J.,Westdijk, Janny,Stork, Michiel,Phalipon, Armelle,Mulard, Laurence A. American Chemical Society 2016 Bioconjugate chemistry Vol.27 No.4
<P>Conjugation chemistry is among the most important parameters governing the efficacy of glycoconjugate vaccines. High robustness is required to ensure high yields and batch to batch reproducibility. Herein, we have established a robust bioconjugation protocol based on the thiol-maleimide addition. Major variables were determined and acceptable margins were investigated for a synthetic pentadecasaccharide-tetanus toxoid conjugate, which is a promising vaccine candidate against Shigella flexneri serotype 2a infection. The optimized process is applicable to any thiol-equipped hapten and provides an efficient control of the hapten:carrier ratio. Moreover, comparison of four S. flexneri 2a glycoconjugates only differing, by their pentadecasaccharide:tetanus toxoid ratio confirmed preliminary findings indicating that hapten loading is critical for immunogenicity with an optimal ratio here in the range of 17 +/- 5. In addition, the powerful influence of alum on the immunogenicity of a Shigella synthetic carbohydrate-based conjugate vaccine candidate is demonstrated for the first time, with a strong anti-S. flexneri 2a antibody response sustained for more than one year.</P>