Single Samarium Atoms in Large Fullerene Cages. Characterization of Two Isomers of Sm@C₉₂ and Four Isomers of Sm@C₉₄ with the X-ray Crystallographic Identification of Sm@<i>C</i>₁(42)-C₉₂, Sm@<i>C</i>_<i>s</i>(24)-C₉₂, and Sm@<i>C</i>_3<i>v</i>(134)-C₉₄

Two isomers of Sm@C₉₂ and four isomers of Sm@C₉₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the Sm@C₉₂ isomers: Sm@C₉₂(I), which is the more abundant isomer, is Sm@<i>C</i>₁(42)-C₉₂, and Sm@C₉₂(II) is Sm@<i>C</i>_<i>s</i>(24)-C₉₂. The structure of the most abundant form of the four isomers of Sm@C₉₄, Sm@C₉₄(I), is Sm@<i>C</i>_3<i>v</i>(134)-C₉₄, which utilizes the same cage isomer as the previously known Ca@<i>C</i>_3<i>v</i>(134)-C₉₄ and Tm@<i>C</i>_3<i>v</i>(134)-C₉₄. All of the structurally characterized isomers obey the isolated pentagon rule. While the four Sm@C₉₀ and five isomers of Sm@C₈₄ belong to common isomerization maps that allow these isomers to be interconverted through Stone–Wales transformations, Sm@<i>C</i>₁(42)-C₉₂ and Sm@<i>C</i>_<i>s</i>(24)-C₉₂ are not related to each other by any set of Stone–Wales transformations. UV–vis–NIR spectroscopy and computational studies indicate that Sm@<i>C</i>₁(42)-C₉₂ is more stable than Sm@<i>C</i>_<i>s</i>(24)-C₉₂ but possesses a smaller HOMO–LUMO gap. While the electronic structures of these endohedrals can be formally described as Sm²⁺@C_2<i>n</i>^2–, the net charge transferred to the cage is less than two due to some back-donation of electrons from π orbitals of the cage to the metal ion

Single Samarium Atoms in Large Fullerene Cages. Characterization of Two Isomers of Sm@C₉₂ and Four Isomers of Sm@C₉₄ with the X-ray Crystallographic Identification of Sm@<i>C</i>₁(42)-C₉₂, Sm@<i>C</i>_<i>s</i>(24)-C₉₂, and Sm@<i>C</i>_3<i>v</i>(134)-C₉₄

Two isomers of Sm@C₉₂ and four isomers of Sm@C₉₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the Sm@C₉₂ isomers: Sm@C₉₂(I), which is the more abundant isomer, is Sm@<i>C</i>₁(42)-C₉₂, and Sm@C₉₂(II) is Sm@<i>C</i>_<i>s</i>(24)-C₉₂. The structure of the most abundant form of the four isomers of Sm@C₉₄, Sm@C₉₄(I), is Sm@<i>C</i>_3<i>v</i>(134)-C₉₄, which utilizes the same cage isomer as the previously known Ca@<i>C</i>_3<i>v</i>(134)-C₉₄ and Tm@<i>C</i>_3<i>v</i>(134)-C₉₄. All of the structurally characterized isomers obey the isolated pentagon rule. While the four Sm@C₉₀ and five isomers of Sm@C₈₄ belong to common isomerization maps that allow these isomers to be interconverted through Stone–Wales transformations, Sm@<i>C</i>₁(42)-C₉₂ and Sm@<i>C</i>_<i>s</i>(24)-C₉₂ are not related to each other by any set of Stone–Wales transformations. UV–vis–NIR spectroscopy and computational studies indicate that Sm@<i>C</i>₁(42)-C₉₂ is more stable than Sm@<i>C</i>_<i>s</i>(24)-C₉₂ but possesses a smaller HOMO–LUMO gap. While the electronic structures of these endohedrals can be formally described as Sm²⁺@C_2<i>n</i>^2–, the net charge transferred to the cage is less than two due to some back-donation of electrons from π orbitals of the cage to the metal ion

sCAR-PPAb binds with SLMAP.

<p>A. sCAR-PPAb combined with a CAR antibody was used in immunoprecipitation. PBS combined with CAR antibody served as the control. Precipitates were analyzed by Western blot for SLMAP. Whole cell lysis (WCL) was monitored for Actin levels. B. SLMAP levels on K562 and K562/ADR were determined by Western blot. Actin served as a loading control. C. A SLMAP antibody enhanced the phagocytosis of K562/ADR by macrophages in vitro. An IgG isotype served as the control. The portion of macrophages ingesting CFSE stained K562/ADR cells was observed under a fluorescence microscope (200 x). A significant enhancement of phagocytosis upon SLMAP antibody treatment was determined (p<0.05).</p

PPA preferentially recognizes drug resistant cancer cells.

<p>A. The sensitivity of K562 and K562/ADR to ADR was determined by a MTT assay. B. K562 or K562/ADR cells were treated with sCAR-PPAb combined with Ad-EGFP or PBS for 48h. The portion of EGFP positive cells was analyzed by flow cytometry. Shown is a representative from 3 separate experiments. C. K562 or K562/ADR cells treated with sCAR-PPAb combined with Ad-EGFP for 48h were examined using a fluorescence microscope. D. The sensitivity of H460 and H460/5Fu to 5Fu was determined by a MTT assay. E. H460 or H460/5Fu cells were treated with sCAR-PPAb combined with Ad-EGFP or PBS for 48h. The portion of EGFP positive cells was analyzed by flow cytometry. Shown is a representative from 3 separate experiments. F. H460 or H460/5Fu cells treated with sCAR-PPAb combined with Ad-EGFP for 48h were examined using a fluorescence microscope.</p

Single Samarium Atoms in Large Fullerene Cages. Characterization of Two Isomers of Sm@C₉₂ and Four Isomers of Sm@C₉₄ with the X-ray Crystallographic Identification of Sm@<i>C</i>₁(42)-C₉₂, Sm@<i>C</i>_<i>s</i>(24)-C₉₂, and Sm@<i>C</i>_3<i>v</i>(134)-C₉₄

Two isomers of Sm@C₉₂ and four isomers of Sm@C₉₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the Sm@C₉₂ isomers: Sm@C₉₂(I), which is the more abundant isomer, is Sm@<i>C</i>₁(42)-C₉₂, and Sm@C₉₂(II) is Sm@<i>C</i>_<i>s</i>(24)-C₉₂. The structure of the most abundant form of the four isomers of Sm@C₉₄, Sm@C₉₄(I), is Sm@<i>C</i>_3<i>v</i>(134)-C₉₄, which utilizes the same cage isomer as the previously known Ca@<i>C</i>_3<i>v</i>(134)-C₉₄ and Tm@<i>C</i>_3<i>v</i>(134)-C₉₄. All of the structurally characterized isomers obey the isolated pentagon rule. While the four Sm@C₉₀ and five isomers of Sm@C₈₄ belong to common isomerization maps that allow these isomers to be interconverted through Stone–Wales transformations, Sm@<i>C</i>₁(42)-C₉₂ and Sm@<i>C</i>_<i>s</i>(24)-C₉₂ are not related to each other by any set of Stone–Wales transformations. UV–vis–NIR spectroscopy and computational studies indicate that Sm@<i>C</i>₁(42)-C₉₂ is more stable than Sm@<i>C</i>_<i>s</i>(24)-C₉₂ but possesses a smaller HOMO–LUMO gap. While the electronic structures of these endohedrals can be formally described as Sm²⁺@C_2<i>n</i>^2–, the net charge transferred to the cage is less than two due to some back-donation of electrons from π orbitals of the cage to the metal ion

Single Samarium Atoms in Large Fullerene Cages. Characterization of Two Isomers of Sm@C₉₂ and Four Isomers of Sm@C₉₄ with the X-ray Crystallographic Identification of Sm@<i>C</i>₁(42)-C₉₂, Sm@<i>C</i>_<i>s</i>(24)-C₉₂, and Sm@<i>C</i>_3<i>v</i>(134)-C₉₄

Two isomers of Sm@C₉₂ and four isomers of Sm@C₉₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the Sm@C₉₂ isomers: Sm@C₉₂(I), which is the more abundant isomer, is Sm@<i>C</i>₁(42)-C₉₂, and Sm@C₉₂(II) is Sm@<i>C</i>_<i>s</i>(24)-C₉₂. The structure of the most abundant form of the four isomers of Sm@C₉₄, Sm@C₉₄(I), is Sm@<i>C</i>_3<i>v</i>(134)-C₉₄, which utilizes the same cage isomer as the previously known Ca@<i>C</i>_3<i>v</i>(134)-C₉₄ and Tm@<i>C</i>_3<i>v</i>(134)-C₉₄. All of the structurally characterized isomers obey the isolated pentagon rule. While the four Sm@C₉₀ and five isomers of Sm@C₈₄ belong to common isomerization maps that allow these isomers to be interconverted through Stone–Wales transformations, Sm@<i>C</i>₁(42)-C₉₂ and Sm@<i>C</i>_<i>s</i>(24)-C₉₂ are not related to each other by any set of Stone–Wales transformations. UV–vis–NIR spectroscopy and computational studies indicate that Sm@<i>C</i>₁(42)-C₉₂ is more stable than Sm@<i>C</i>_<i>s</i>(24)-C₉₂ but possesses a smaller HOMO–LUMO gap. While the electronic structures of these endohedrals can be formally described as Sm²⁺@C_2<i>n</i>^2–, the net charge transferred to the cage is less than two due to some back-donation of electrons from π orbitals of the cage to the metal ion

Isolation of Three Isomers of Sm@C₈₄ and X-ray Crystallographic Characterization of Sm@<i>D</i>_3<i>d</i>(19)-C₈₄ and Sm@<i>C</i>₂(13)-C₈₄

Three isomers with the composition Sm@C₈₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. These isomers were labeled Sm@C₈₄(I), Sm@C₈₄(II), and Sm@C₈₄(III) in order of their elution times during chromatography on a Buckyprep column with toluene as the eluent. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the isomers: Sm@C₈₄(I) is Sm@<i>C</i>₂(13)-C₈₄, and Sm@C₈₄(III) is Sm@ <i>D</i>_3<i>d</i>(19)-C₈₄. Sm@C₈₄(II) can be identified as Sm@<i>C</i>₂(11)-C₈₄ on the basis of the similarity of its UV/vis/NIR spectrum with that of Yb@<i>C</i>₂(11)-C₈₄, whose carbon cage has been characterized by ¹³C NMR spectroscopy. Comparison of the three Sm@C₈₄ isomers identified in this project with two prior reports of the preparation and isolation of isomers of Sm@C₈₄ indicate that five different Sm@C₈₄ isomers have been found and that the source of samarium used for the generation of fullerene soot is important in determining which of these isomers form

sCAR-PPAb enhances the phagocytosis of K562/ADR cells by macrophages in vivo.

<p>A. sCAR-PPAb did not enhance the phagocytosis of K562 cells by macrophages. K562 cells stained with CFSE and pretreated with sCAR-PPAb or PBS were injected into the abdominal cavity in ICR mice. After 5h, cells in the abdominal cavity were then collected and stained with a primary antibody against F4/80 or IgG isotype followed by a goat anti-rat IgG-PE antibody. Cells were then analyzed by flow cytometry. Data were reported as the percent of macrophages undergoing phagocytosis, calculated by CFSE/PE double positive cells divided by all PE positive cells. Values are shown as mean ± SEM (p>0.05, n=3). B. sCAR-PPAb enhanced the phagocytosis of K562/ADR by macrophages. Data were reported as the percent of macrophages undergoing phagocytosis, calculated by CFSE/PE double positive cells divided by all PE positive cells. Values are shown as mean ± SEM (p<0.05, n=3). C. The cytotoxicity of sCAR-PPAb on K562 and K562/ADR was analyzed by MTT assay. D. Mouse macrophages from the abdominal cavity were isolated and cultured in 96-well plates. The cells were then treated with 5μg of sCAR-PPAb for 5 hours. PBS treatment served as the control. The cell viability was analyzed by MTT assay.</p

sCAR-PPAb activated macrophages in a K562/ADR xenograft model.

<p>BALB/c nude mice were transplanted with K562/ADR cells subcutaneously. sCAR-PPAb were injected intratumorally for 7 days at 100μg/day. PBS injection served as the control. A. Tumors were harvested and F4/80 was analyzed for macrophage infiltration by immunohistochemistry. The control showed IgG isotype staining. Arrows point to cells stained with F4/80. Bars show 200μm (400 x). B. Tumors were analyzed using a transmission electron microscope. The arrow points to cells undergoing phagocytosis. Bars show 2μm.</p

Isolation of Three Isomers of Sm@C₈₄ and X-ray Crystallographic Characterization of Sm@<i>D</i>_3<i>d</i>(19)-C₈₄ and Sm@<i>C</i>₂(13)-C₈₄

Three isomers with the composition Sm@C₈₄ were isolated from carbon soot obtained by electric arc vaporization of carbon rods doped with Sm₂O₃. These isomers were labeled Sm@C₈₄(I), Sm@C₈₄(II), and Sm@C₈₄(III) in order of their elution times during chromatography on a Buckyprep column with toluene as the eluent. Analysis of the structures by single-crystal X-ray diffraction on cocrystals formed with Ni^II(octaethylporphyrin) reveals the identities of two of the isomers: Sm@C₈₄(I) is Sm@<i>C</i>₂(13)-C₈₄, and Sm@C₈₄(III) is Sm@ <i>D</i>_3<i>d</i>(19)-C₈₄. Sm@C₈₄(II) can be identified as Sm@<i>C</i>₂(11)-C₈₄ on the basis of the similarity of its UV/vis/NIR spectrum with that of Yb@<i>C</i>₂(11)-C₈₄, whose carbon cage has been characterized by ¹³C NMR spectroscopy. Comparison of the three Sm@C₈₄ isomers identified in this project with two prior reports of the preparation and isolation of isomers of Sm@C₈₄ indicate that five different Sm@C₈₄ isomers have been found and that the source of samarium used for the generation of fullerene soot is important in determining which of these isomers form