Immunogenic Cell Death of Breast Cancer Stem Cells by an Endoplasmic Reticulum-Targeting Copper(II) Complex.

Immunogenic cell death (ICD) offers a method of stimulating the immune system to attack and remove cancer cells. We report a copper(II) complex containing a Schiff base ligand and a polypyridyl ligand, 4 capable of inducing ICD in breast cancer stem cells (CSCs). The complex, 4 kills both bulk breast cancer cells and breast CSCs in the sub-micromolar range. Notably, 4 exhibits greater potency (one order of magnitude) towards breast CSCs than salinomycin (an established breast CSC-potent agent) and cisplatin (a clinically approved anticancer drug). Epithelial spheroid studies show that 4 is able to selectively inhibit breast CSC-enriched HMLER-shEcad spheroid formation and viability over non-tumorigenic breast MCF10A spheroids. Mechanistic studies show that 4 operates as a Type II ICD inducer. Specifically, 4 readily enters the endoplasmic reticulum (ER) of breast CSCs, elevates intracellular reactive oxygen species (ROS) levels, induces ER stress, evokes damage-associated molecular patterns (DAMPs), and promotes breast CSC phagocytosis by macrophages. As far as we are aware, 4 is the first metal complex to induce ICD in breast CSCs and promote their engulfment by immune cells

Detection of a Family of Gadolinium-Containing Endohedral Fullerenes and the Isolation and Crystallographic Characterization of One Member as a Metal−Carbide Encapsulated inside a Large Fullerene Cage

A series of di-gadolinium endohedrals that extends from Gd2C90 to Gd2C124 has been detected by mass spectrometry of the o-dichlorobenzene extract of the carbon soot produced by direct current arcing of graphite rods filled with a mixture of Gd2O3 and graphite powder. Chromatographic separation has led to the isolation of pure samples of two isomers of Gd2C94 and the complete series from Gd2C96 to Gd2C106. Endohedral fullerenes of the type M2C2n can exist as the conventional endohedral, M2@C2n, or as the carbide-containing endohedral, M2C2@C2n−2. Crystallographic characterization of the more rapidly eluting isomer of Gd2C94 reveals that it possesses the carbide structure, Gd2C2@D3(85)-C92. Computational studies suggest that the more slowly eluting isomer of Gd2C94 may be a conventional endohedral, Gd2@C2(121)-C94

Detection of a Family of Gadolinium-Containing Endohedral Fullerenes and the Isolation and Crystallographic Characterization of One Member as a Metal−Carbide Encapsulated inside a Large Fullerene Cage

A series of di-gadolinium endohedrals that extends from Gd2C90 to Gd2C124 has been detected by mass spectrometry of the o-dichlorobenzene extract of the carbon soot produced by direct current arcing of graphite rods filled with a mixture of Gd2O3 and graphite powder. Chromatographic separation has led to the isolation of pure samples of two isomers of Gd2C94 and the complete series from Gd2C96 to Gd2C106. Endohedral fullerenes of the type M2C2n can exist as the conventional endohedral, M2@C2n, or as the carbide-containing endohedral, M2C2@C2n−2. Crystallographic characterization of the more rapidly eluting isomer of Gd2C94 reveals that it possesses the carbide structure, Gd2C2@D3(85)-C92. Computational studies suggest that the more slowly eluting isomer of Gd2C94 may be a conventional endohedral, Gd2@C2(121)-C94

Revealing the Intrinsic Nature of the Synergistic Effect Caused by the Formation of Heterojunctions in Cu–Cu₂O/rGO-NH₂ Nanomaterials in the Catalysis of Selective Aerobic Oxidation of Benzyl Alcohol

Ternary nanomaterials Cu–Cu2O/rGO-NH2 (rGO = reduced graphene oxide) exhibited a synergistic effect in the quantitative catalysis of selective aerobic oxidation of benzyl alcohol. The synergistic effect is attributed to the heterojunctions among the three components and in intrinsic nature, the formation of the heterojunctions lowered the conduction band (CB) energy level and raised the valence band (VB) energy level of the main catalyst Cu2O, which eases electron transfer from the catalyst to O2 in its activation and from the substrate to the catalyst in the oxidation, respectively

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@<i>C</i>_3<i>v</i>-C₉₄ and Ca@<i>C</i>_3<i>v</i>-C₉₄

The structures of two newly synthesized endohedral fullerenes, Tm@C3v-C94 and Ca@C3v-C94, have been determined by single crystal X-ray diffraction on samples cocrystallized with NiII(octaethylporphyrin). Both compounds exhibit the same cage geometry and conform to the isolated pentagon rule (IPR). The metal ions within these rather large cages are localized near one end and along the C3 axis. While the calcium ion is situated over a C−C bond at a 6:6 ring junction, the thulium ion is positioned above a six-membered ring of the fullerene

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@<i>C</i>_3<i>v</i>-C₉₄ and Ca@<i>C</i>_3<i>v</i>-C₉₄

The structures of two newly synthesized endohedral fullerenes, Tm@C3v-C94 and Ca@C3v-C94, have been determined by single crystal X-ray diffraction on samples cocrystallized with NiII(octaethylporphyrin). Both compounds exhibit the same cage geometry and conform to the isolated pentagon rule (IPR). The metal ions within these rather large cages are localized near one end and along the C3 axis. While the calcium ion is situated over a C−C bond at a 6:6 ring junction, the thulium ion is positioned above a six-membered ring of the fullerene