Solvent Effects upon Guest Binding and Dynamics of a Fe^II₄L₄ Cage

Solvent-dependent host–guest chemistry and favoring of otherwise disfavored conformations of large guests has been achieved with an adaptive, self-assembled Fe^II₄L₄ coordination cage. Depending on the counterion, this face-capped tetrahedral capsule is soluble either in water or in acetonitrile and shows a solvent-dependent preference for encapsulation of certain classes of guest molecules. Quantitative binding studies were undertaken, revealing that both aromatic and aliphatic guests bind in water, whereas only aliphatic guests bind in acetonitrile. The flexibility of its subcomponent building blocks allows this cage to expand or contract upon guest binding, as studied by VT-NMR, thereby ensuring strong binding of both small and large guests. Upon encapsulation, large guest molecules can adopt conformations which are not thermodynamically favored in the free state. In addition, the chirotopic inner phase of the cage renders enantiotopic guest proton signals diastereotopic in specific cases

Synthesis and Cavity Size Effect of Pd-Containing Macrocycle Catalyst for Efficient Intramolecular Hydroamination of Allylurethane

Palladium-containing macrocycle catalysts (<b>PdMCs</b>) with different ring sizes ranging from 24 to 30 members were synthesized. The intramolecular hydroamination of an allylurethane (<b>AU</b>) catalyzed by <b>PdMCs</b> proceeded efficiently to afford the corresponding oxazolidinone (<b>OZ</b>) in 95% isolated yield. The dependence of the hydroamination of <b>AU</b> to <b>OZ</b> on the cavity size indicated that the reaction rate was clearly controlled by both substrate uptake and product release steps

Solvent Effects upon Guest Binding and Dynamics of a Fe^II₄L₄ Cage

Solvent-dependent host–guest chemistry and favoring of otherwise disfavored conformations of large guests has been achieved with an adaptive, self-assembled Fe^II₄L₄ coordination cage. Depending on the counterion, this face-capped tetrahedral capsule is soluble either in water or in acetonitrile and shows a solvent-dependent preference for encapsulation of certain classes of guest molecules. Quantitative binding studies were undertaken, revealing that both aromatic and aliphatic guests bind in water, whereas only aliphatic guests bind in acetonitrile. The flexibility of its subcomponent building blocks allows this cage to expand or contract upon guest binding, as studied by VT-NMR, thereby ensuring strong binding of both small and large guests. Upon encapsulation, large guest molecules can adopt conformations which are not thermodynamically favored in the free state. In addition, the chirotopic inner phase of the cage renders enantiotopic guest proton signals diastereotopic in specific cases

Isolation of Hypervalent Group-16 Radicals and Their Application in Organic-Radical Batteries

Using a newly prepared tridentate ligand, we isolated hypervalent sulfur and selenium radicals for the first time and characterized their structures. X-ray crystallography, electron spin resonance spectroscopy, and density functional theory calculations revealed a three-coordinate hypervalent structure. Utilizing the reversible redox reactions between hypervalent radicals and the corresponding anions bearing Li⁺, we developed organic radical batteries with these compounds as cathode-active materials. Furthermore, an all-radical battery, with these compounds as the cathode and a silyl radical as the anode, was developed that exhibited a practical discharge potential of ∼1.8 V and stable cycle performance, demonstrating the potential of these materials for use in metal-free batteries that can replace conventional Li-ion batteries where Li is used in the metal form

TCR-stimulation induced Egr expressions were impaired in the <i>Zfat</i>-deficient DP thymocytes.

<p>(A)Immunoblots for Egr1, Egr2 and Egr3 before or at the indicated time points after the stimulation with plate-bound anti-CD3ε and anti-CD28 antibodies in DP cells from the indicated genotypes. Actin was used as a loading control. Data are representative of three independent experiments. (B) Immunoblots for Egr1, Egr2 and Egr3 in DP cells from the indicated genotypes before or at the indicated time points after the stimulation with plate-bound anti-CD3ε and anti-CD28 antibodies under the condition with U0126 in DMSO or with DMSO alone. Actin was used as a loading control. Data are representative of three independent experiments. (C, D) Quantitative RT-PCR analysis of <i>Egr1</i>, <i>Egr2</i> and <i>Egr3</i> expression before (C) or at the indicated time points after the stimulation with anti-CD3ε and anti-CD28 antibodies (D) in DP cells from <i>Zfat</i>^f/f and <i>Zfat</i>^f/f-<i>LckCre</i> mice. The relative expression for each gene was normalized by the expression of <i>Actb</i>. The results are presented as the value relative to the unstimulated DP cells from <i>Zfat</i>^f/f mice. The data are the mean ± s.d.; n.s., not significant.</p

Reduction in the number of thymocytes and peripheral T cells in <i>Zfat</i>^f/f-<i>LckCre</i> mice.

<p>(A) An immunoblot of Zfat in nuclear (N) or cytoplasmic (C) fractions of thymocytes from <i>Zfat</i>^f/f and <i>Zfat</i>^f/f-<i>LckCre</i> mice. CREB1 and PLCγ1 were used as controls of nuclear and cytoplasmic fractions, respectively. (B) An immunoblot of Zfat in DN1 and DN2 (DN1,2: CD4⁻CD8⁻CD44⁺), DN3 (CD4⁻CD8⁻CD25⁺CD44⁻), DN4 (CD4⁻CD8⁻CD25⁻CD44⁻) or DP thymocytes from <i>Zfat</i>^f/f and <i>Zfat</i>^f/f-<i>LckCre</i> mice. Actin was used as a loading control. (C) Flow cytometry analysis of the surface expression of CD4 and CD8 on thymocytes from <i>Zfat</i>^f/f (top) and <i>Zfat</i>^f/f-<i>LckCre</i> (bottom) mice at 6 to 7 weeks of age. Data are representative of three independent experiments. (D) Total numbers of thymocytes, thymic DP, DN, CD4SP or CD8SP cells from <i>Zfat</i>^f/f (black bars) and <i>Zfat</i>^f/f-<i>LckCre</i> (white bars) mice at 6 to 7 weeks of age. The data are the mean ± standard deviation (s.d.); <i>n</i> = 6; * <i>P</i><0.05; ** <i>P</i><0.01; n.s., not significant. (E) Flow cytometry analysis of TCRβ⁺T cells and B220⁺B cells (left) or CD4⁺and CD8⁺T cells (right) in the spleen and LNs of <i>Zfat</i>^f/f (top) and <i>Zfat</i>^f/f-<i>LckCre</i> (bottom) mice. Data are representative of three independent experiments. (F) Total numbers of CD4⁺T, CD8⁺T or B220⁺B cells in the spleen from <i>Zfat</i>^f/f (black bars) and <i>Zfat</i>^f/f-<i>LckCre</i> (white bars) mice. The data are the mean ± s.d.; <i>n</i> = 6; ** <i>P</i><0.01; n.s., not significant.</p