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Ley, Morten B.,Ravnsbæk, Dorthe B.,Filinchuk, Yaroslav,Lee, Young-Su,Janot, Raphaë,l,Cho, Young Whan,Skibsted, Jørgen,Jensen, Torben R. American Chemical Society 2012 Chemistry of materials Vol.24 No.9
<P>Mechanochemical synthesis using CeCl<SUB>3</SUB>-MBH<SUB>4</SUB> (M = Li, Na or K) mixtures are investigated and produced a new compound, LiCe(BH<SUB>4</SUB>)<SUB>3</SUB>Cl, which crystallizes in a cubic space group <I>I</I>4̅3<I>m</I>, <I>a</I> = 11.7204(2) Å. The structure contains isolated tetranuclear anionic clusters [Ce<SUB>4</SUB>Cl<SUB>4</SUB>(BH<SUB>4</SUB>)<SUB>12</SUB>]<SUP>4–</SUP> with a distorted cubane Ce<SUB>4</SUB>Cl<SUB>4</SUB> core, charge-balanced by Li<SUP>+</SUP> cations. Each Ce atom coordinates three chloride ions and three borohydride groups via the η<SUP>3</SUP>–BH<SUB>3</SUB> faces, thus completing the coordination environment to an octahedron. Combination of synchrotron radiation powder X-ray diffraction (SR-PXD), powder neutron diffraction and density functional theory (DFT) optimization show that Li cations are disordered, occupying 2/3 of the 12<I>d</I> Wyckoff site. DFT calculation indicates that LiCe(BH<SUB>4</SUB>)<SUB>3</SUB>Cl is stabilized by higher entropy rather than lower enthalpy, in accord with the disorder in Li positions. The structural model also agrees well with the very high lithium ion conductivity measured for LiCe(BH<SUB>4</SUB>)<SUB>3</SUB>Cl of 1 × 10<SUP>–4</SUP> Scm<SUP>–1</SUP> at <I>T</I> = 20 °C. In situ SR-PXD reveals that the decomposition products consist of LiCl, CeB<SUB>6</SUB> and CeH<SUB>2</SUB>. The Sieverts measurements show that 4.7 wt % H<SUB>2</SUB> is released during heating to 500 °C. After rehydrogenation at 400 °C and <I>p</I>(H<SUB>2</SUB>) = 100 bar for 24 h an amount of 1.8 wt % H<SUB>2</SUB> is released in the second dehydrogenation. The <SUP>11</SUP>B MAS NMR spectra of the central and satellite transitions for LiCe(B(D/H)<SUB>4</SUB>)<SUB>3</SUB>Cl reveal highly asymmetric manifolds of spinning sidebands from a single <SUP>11</SUP>B site, reflecting dipolar couplings of the <SUP>11</SUP>B nuclear spin with the paramagnetic electron spin of the Ce<SUP>3+</SUP> ions.</P><P>A new type of energy storage materials is discovered, LiCe(BH<SUB>4</SUB>)<SUB>3</SUB>Cl, which contains hydrogen and simultaneously is a fast lithium ion conductor. The fascinating entropy stabilized structure contains isolated tetranuclear anionic clusters [Ce<SUB>4</SUB>Cl<SUB>4</SUB>(BH<SUB>4</SUB>)<SUB>12</SUB>]<SUB>4−</SUB> with a distorted cubane Ce<SUB>4</SUB>Cl<SUB>4</SUB> core, charge-balanced by disordered Li+ cations occupying 2/3 of the crystallographic position.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cmatex/2012/cmatex.2012.24.issue-9/cm300792t/production/images/medium/cm-2012-00792t_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/cm300792t'>ACS Electronic Supporting Info</A></P>
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Nanofiber Scaffolds by Electrospinning for Rotator Cuff Tissue Engineering
임태강,Erik Dorthé,Austin Williams,Darryl D D’Lima 전남대학교 의과학연구소 2021 전남의대학술지 Vol.57 No.1
Rotator cuff tears continue to be at risk of retear or failure to heal after surgical repair, despite the use of various surgical techniques, which stimulate development of novel scaffolding strategies. They should be able to address the known causes of failure after the conventional rotator cuff repair: (1) failure to reproduce the normal tendon healing process, (2) resultant failure to reproduce four zones of the enthesis, and (3) failure to attain sufficient mechanical strength after repair. Nanofiber scaffolds are suited for this application because they can be engineered to mimic the ultrastructure and properties of the native rotator cuff tendon. Among various methods for tissue-engineered nanofibers, electrospinning has recently been highlighted in the rotator cuff field. Electrospinning can create fibrous and porous structures that resemble natural tendon’s extracellular matrix. Other advantages include the ability to create relatively large surface-to-volume ratios, the ability to control fiber size from the micro to the nano scale, and the flexibility of material choices. In this review, we will discuss the anatomical and mechanical features of the rotator cuff tendon, their potential impacts on improper healing after repair, and the current knowledge of the use of electrospinning for rotator cuff tissue engineering.
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