Cobalt bisdicarbollides (COSANs) are inorganic boron-based anions that have been previously reported to permeate by themselves through lipid bilayer membranes, a propensity that is related to their superchaotropic character. We now introduce their use as selective and efficient molecular carriers of otherwise impermeable hydrophilic oligopeptides through both artificial and cellular membranes, without causing membrane lysis or poration at low micromolar carrier concentrations. COSANs transport not only arginine-rich but also lysine-rich peptides, whereas low-molecular-weight analytes such as amino acids as well as neutral and anionic cargos (phalloidin and BSA) are not transported. In addition to the unsubstituted isomers (known as ortho- and meta-COSAN), four derivatives bearing organic substituents or halogen atoms have been evaluated, and all six of them surpass established carriers such as pyrenebutyrate in terms of activity. U-tube experiments and black lipid membrane conductance measurements establish that the transport across model membranes is mediated by a molecular carrier mechanism. Transport experiments in living cells showed that a fluorescent peptide cargo, FITC-Arg8, is delivered into the cytosol.

Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares Universidade de Santiago de Compostela Jenaro de la Fuente s n 15782 Santiago de Compostela Spain

Institute of Inorganic Chemistry Czech Academy of Sciences v v i Hlavní 1001 CZ 250 68 Řež Czech Republic

School of Science Constructor University Campus Ring 1 28759 Bremen Germany

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We introduce here (top panels f and g) the “arrow-notation” for ITC titrations, where the compound on the top corresponds to the compound in the syringe, which is being added (arrow) to the compound contained in the cell (bottom); the additional advantage of this notation is that the top and bottom compounds correspond directly, written as a fraction with nominator and denominator, to the stoichiometric n value obtained from the ITC experiment, e.g., 2/protamine = 17.

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Carbon-Substituted Amines of the Cobalt Bis(dicarbollide) Ion: Stereochemistry and Acid-Base Properties

Chemistry of Carbon-Substituted Derivatives of Cobalt Bis(dicarbollide)(1-) Ion and Recent Progress in Boron Substitution