The interaction of amino acids with macrocyclic pH probes of pseudopeptidic nature.

The fluorescence quenching, by a series of amino acids, of pseudopeptidic compounds acting as probes for cellular acidity has been investigated. It has been found that amino acids containing electron-rich aromatic side chains like Trp or Tyr, as well as Met quench the emission of the probes mainly via a collisional mechanism, with Stern-Volmer constants in the 7-43 M range, while other amino acids such as His, Val or Phe did not cause deactivation of the fluorescence. Only a minor contribution of a static quenching due to the formation of ground-state complexes has been found for Trp and Tyr, with association constants in the 9-24 M range.

Cobalt polyoxometalates as heterogeneous water oxidation catalysts.

An insoluble salt of the water oxidation catalyst [Co9(H2O)6(OH)3(HPO4)2(PW9O34)3](16-) (Co9) has been used to modify amorphous carbon paste electrodes. The catalytic activity of this polyoxometalate is maintained in the solid state. Good catalytic rates are reached at reasonable overpotentials.

Identification of a nonanuclear {Co(II)9} polyoxometalate cluster as a homogeneous catalyst for water oxidation.

The polyanion of formula {Co(9)(H(2)O)(6)(OH)(3)(HPO(4))(2)(PW(9)O(34))(3)}(16-) (Co(9)) contains a central nonacobalt core held together by hydroxo and hydrogen phosphate bridges and supported by three lacunary Keggin-type polyphosphotungstate ligands. Our data demonstrate that Co(9) is a homogeneous catalyst for water oxidation. Catalytic water electrolysis on fluorine-doped tin oxide coated glass electrodes occurs at reasonable low overpotentials and rates when Co(9) is present in a sodium phosphate buffer solution at neutral pH.

Triplet excited state behavior of naphthalene-based pseudopeptides in the presence of energy donors.

In this work, the triplet state behavior of naphthalene-based pseudopeptides with amide-based macrocyclic or lateral chain substructures has been investigated in the presence of benzophenone and/or biphenyl, as suitable energy-donating chromophores. Their behavior has been compared with that of 1,4-dimethylnaphthalene as model compound. In all the cases, the triplet-triplet absorption of naphthalene is detected by transient absorption spectroscopy, upon selective excitation of benzophenone at 355 nm.

Electronic structure of oxidized complexes derived from cis-[Ru(II)(bpy)2(H2O)2]2+ and its photoisomerization mechanism.

The geometry and electronic structure of cis-[Ru(II)(bpy)(2)(H(2)O)(2)](2+) and its higher oxidation state species up formally to Ru(VI) have been studied by means of UV-vis, EPR, XAS, and DFT and CASSCF/CASPT2 calculations. DFT calculations of the molecular structures of these species show that, as the oxidation state increases, the Ru-O bond distance decreases, indicating increased degrees of Ru-O multiple bonding. In addition, the O-Ru-O valence bond angle increases as the oxidation state increases.

Tunable single-site ruthenium catalysts for efficient water oxidation.

The catalytic water oxidation activity of mononuclear ruthenium complexes comprising a pyridine-functionalized abnormal triazolylidene ligand can be adjusted by modification of the triazolylidene substituents, which is readily achieved through click-type cycloaddition chemistry, affording some of the most active ruthenium catalysts known thus far for water oxidation (TONs > 400, TOFs close to 7000 h(-1)).

Oxygen-oxygen bond formation pathways promoted by ruthenium complexes.

The photoproduction of hydrogen from water and sunlight represents an attractive means of artificial energy conversion for a world still largely dependent on fossil fuels. A practical technology for producing sun-derived hydrogen remains an unachieved goal, however, and is dependent on developing a better understanding of the key reaction, the oxidation of water to dioxygen. The molecular complexity of this process is such that sophisticated transition metal complexes, which can access low-energy reaction pathways, are considered essential as catalysts.

Unraveling the molecular recognition of amino acid derivatives by a pseudopeptidic macrocycle: ESI-MS, NMR, fluorescence, and modeling studies.

The binding between a pseudopeptidic macrocyclic naphthalenophane and different N-protected amino acid derivatives has been thoroughly studied by ESI-MS, NMR, fluorescence, and molecular modeling. Careful NMR titration experiments led to the characterization of the intermolecular noncovalent interactions, reflecting a slight side chain and l-stereoselectivity of the host-guest complexes. The data suggest the formation of an intimate ionic pair after the proton transfer from the carboxylic substrate to the amino macrocycle.

Molecular rotors as simple models to study amide NH-aromatic interactions and their role in the folding of peptide-like structures.

The conformational behavior of designed macrocyclic naphthalenophanes (1a,b and 2a,b) derived from amino acids (Phe and Val) has been used for studying NH...

A turn-on fluorescent indicator for citrate with micromolar sensitivity.

A turn-on fluorescent indicator for citric acid (citrate) has been developed, displaying high emission enhancement (+1500%) and low interference by other carboxylates. The sensor is based on the non-emissive copper(II) complex of a fluorescent amino amide, which, upon addition of citrate decomplexates to yield the emissive ligand. The detection limit estimated for this new chemosensing system is about 0.