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      • Ductular reaction is helpful in defining early stromal invasion, small hepatocellular carcinomas, and dysplastic nodules

        Park, Young Nyun,Kojiro, Masamichi,Di Tommaso, Luca,Dhillon, Amar P.,Kondo, Fukuo,Nakano, Masayuki,Sakamoto, Michiie,Theise, Neil D.,Roncalli, Massimo John Wiley & Sons 2007 Cancer Vol.109 No.5

        <B>BACKGROUND.</B><P>Stromal invasion is 1 of the main features used to distinguish high-grade dysplastic nodules (DNs) from well-differentiated hepatocellular carcinomas (HCCs). The authors hypothesized that ductular reaction (DR) takes place around noninvasive hepatocellular nodules but not within the stroma contiguous to invasive HCC.</P><B>METHODS.</B><P>DR/cytokeratin 7 (CK7)-positive patterns were evaluated in 105 resected small hepatic nodules according to the level of invasion. The nodules were classified histologically prior to immunostaining as noninvasive (large regenerative nodules, low-grade DNs, and high-grade DNs), minimally invasive (early HCCs with a vaguely nodular type), and overtly invasive (typical HCCs with a distinctly nodular type) in a review by expert pathologists, the current gold standard. Intranodular DR (inner DR) and DR around the nodule periphery (outer DR) were assessed separately on a semiquantitative scale from 0 to 4+.</P><B>RESULTS.</B><P>DR was 3 or 4+ in the majority of noninvasive nodules (inner DR, 81%; outer DR, 91%), whereas DR was 0 or 1+ in overtly invasive HCCs (inner DR, 96%; outer DR, 81%). Minimally invasive HCCs showed an intermediate DR pattern (2 or 3+ inner DR, 75%; 2+ outer DR, 67%). DR characteristically was absent at the stromal-invasive, leading edge of tumor cells in both minimally invasive HCCs (focal loss of DR/CK7) and overtly invasive HCCs (diffuse loss of DR/CK7). The DR patterns in 41 needle-biopsy samples were similar to the patterns observed in resected nodules.</P><B>CONCLUSIONS.</B><P>DR/CK7 immunostaining may help to identify small foci of invasion and to distinguish noninvasive, high-grade DNs from both minimally invasive and overtly invasive HCCs. Cancer 2007 © 2007 American Cancer Society.</P>

      • KF and CsF Recognition and Extraction by a Calix[4]crown-5 Strapped Calix[4]pyrrole Multitopic Receptor

        Kim, Sung Kuk,Lynch, Vincent M.,Young, Neil J.,Hay, Benjamin P.,Lee, Chang-Hee,Kim, Jong Seung,Moyer, Bruce A.,Sessler, Jonathan L. American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.51

        <P>On the basis of <SUP>1</SUP>H NMR spectroscopic analyses and single crystal X-ray crystal structural data, the ion-pair receptor <B>1</B>, bearing a calix[4]pyrrole for anion binding and calix[4]arene crown-5 for cation recognition, was found to act as a receptor for both CsF and KF ion-pairs. Both substrates are bound strongly but via different binding modes and with different complexation dynamics. Specifically, exposure to KF in 10% CD<SUB>3</SUB>OD in CDCl<SUB>3</SUB> leads first to complexation of the K<SUP>+</SUP> cation by the calix[4]arene crown-5 moiety. As the relative concentration of KF increases, then the calix[4]pyrrole subunit binds the F<SUP>–</SUP> anion. Once bound, the K<SUP>+</SUP> cation and the F<SUP>–</SUP> anion give rise to a stable 1:1 ion-pair complex that generally precipitates from solution. In contrast to what is seen with KF, the CsF ion-pair interacts with receptor <B>1</B> in two different modes in 10% CD<SUB>3</SUB>OD in CDCl<SUB>3</SUB>. In the first of these, the Cs<SUP>+</SUP> cation interacts with the calix[4]arene crown-5 ring weakly. In the second interaction mode, which is thermodynamically more stable, the Cs<SUP>+</SUP> cation and the counteranion, F<SUP>–</SUP>, are simultaneously bound to the receptor framework. Further proof that system <B>1</B> acts as a viable ion-pair receptor came from the finding that receptor <B>1</B> could extract KF from an aqueous phase into nitrobenzene, overcoming the high hydration energies of the K<SUP>+</SUP> and F<SUP>–</SUP> ions. It was more effective in this regard than a 1:1 mixture of the constituent cation and anion receptors (<B>4</B> and <B>5</B>).</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2012/jacsat.2012.134.issue-51/ja310673p/production/images/medium/ja-2012-10673p_0009.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja310673p'>ACS Electronic Supporting Info</A></P>

      • Controlling Cesium CationRecognition via Cation Metathesiswithin an Ion Pair Receptor

        Kim, Sung Kuk,Vargas-Zú,,iga, GabrielaI.,Hay, Benjamin P.,Young, Neil J.,Delmau, Lætitia H.,Masselin, Charles,Lee, Chang-Hee,Kim, Jong Seung,Lynch, VincentM.,Moyer, Bruce A.,Sessler, Jona American Chemical Society 2012 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.134 No.3

        <P>Ion pair receptor 3 bearing an anion binding site and multiple cation binding sites has been synthesized and shown to function in a novel binding-release cycle that does not necessarily require displacement to effect release. The receptor forms stable complexes with the test cesium salts, CsCl and CsNO3, in solution (10% methanol-d(4) in chloroform-d) as inferred from H-1 NMR spectroscopic analyses. The addition of KClO4 to these cesium salt complexes leads to a novel type of cation metathesis in which the 'exchanged' cations occupy different binding sites. Specifically, K+ becomes bound at the expense of the Cs+ cation initially present in the complex. Under liquid liquid conditions, receptor 3 is able to extract CsNO3 and CsCl from an aqueous D2O layer into nitrobenzene-d(5) as inferred from H-1 NMR spectroscopic analyses and radiotracer measurements. The Cs+ cation of the CsNO3 extracted into the nitrobenzene phase by receptor 3 may be released into the aqueous phase by contacting the loaded nitrobenzene phase with an aqueous KClO4 solution. Additional exposure of the nitrobenzene layer to chloroform and water gives 3 in its uncomplexed, ion-free form. This allows receptor 3 to be recovered for subsequent use. Support for the underlying complexation chemistry came from single-crystal X-ray diffraction analyses and gas-phase energy-minimization studies.</P>

      • Multiscale Engineered Si/SiO<i><sub>x</sub></i> Nanocomposite Electrodes for Lithium-Ion Batteries Using Layer-by-Layer Spray Deposition

        Huang, Chun,Kim, Ayoung,Chung, Dong Jae,Park, Eunjun,Young, Neil P.,Jurkschat, Kerstin,Kim, Hansu,Grant, Patrick S. American Chemical Society 2018 ACS APPLIED MATERIALS & INTERFACES Vol.10 No.18

        <P>Si-based high-capacity materials have gained much attention as an alternative to graphite in Li-ion battery anodes. Although Si additions to graphite anodes are now commercialized, the fraction of Si that can be usefully exploited is restricted due to its poor cyclability arising from the large volume changes during charge/discharge. Si/SiO<I><SUB>x</SUB></I> nanocomposites have also shown promising behavior, such as better capacity retention than Si alone because the amorphous SiO<I><SUB>x</SUB></I> helps to accommodate the volume changes of the Si. Here, we demonstrate a new electrode architecture for further advancing the performance of Si/SiO<I><SUB>x</SUB></I> nanocomposite anodes using a scalable layer-by-layer atomization spray deposition technique. We show that particulate C interlayers between the current collector and the Si/SiO<I><SUB>x</SUB></I> layer and between the separator and the Si/SiO<I><SUB>x</SUB></I> layer improved electrical contact and reduced irreversible pulverization of the Si/SiO<I><SUB>x</SUB></I> significantly. Overall, the multiscale approach based on microstructuring at the electrode level combined with nanoengineering at the material level improved the capacity, rate capability, and cycling stability compared to that of an anode comprising a random mixture of the same materials.</P> [FIG OMISSION]</BR>

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