Anti-Inflammatory Chilean Endemic Plants.

Medicinal plants have been used since prehistoric times and continue to treat several diseases as a fundamental part of the healing process. Inflammation is a condition characterized by redness, pain, and swelling. This process is a hard response by living tissue to any injury. Furthermore, inflammation is produced by various diseases such as rheumatic and immune-mediated conditions, cancer, cardiovascular diseases, obesity, and diabetes. Hence, anti-inflammatory-based treatments could emerge as a novel and exciting approach to treating these diseases. Medicinal plants and their secondary metabolites are known for their anti-inflammatory properties, and this review introduces various native Chilean plants whose anti-inflammatory effects have been evaluated in experimental studies. Fragaria chiloensis, Ugni molinae, Buddleja globosa, Aristotelia chilensis, Berberis microphylla, and Quillaja saponaria are some native species analyzed in this review. Since inflammation treatment is not a one-dimensional solution, this review seeks a multidimensional therapeutic approach to inflammation with plant extracts based on scientific and ancestral knowledge.

Molecular and Electronic Structure, and Hydrolytic Reactivity of a Samarium(II) Crown Ether Complex.

The reaction of SmI2 with dibenzo-30-crown-10 (DB30C10), followed by metathesis with [Bu4N][BPh4], allows for the isolation of [SmII(DB30C10)][BPh4]2 as bright-red crystals in good yield. Exposure of [Sm(DB30C10)]2+ to solvents containing trace water results in the conversion to the dinuclear SmIII complex, Sm2(DB30C10)(OH)2I4. Structural analysis of both complexes shows substantial rearrangement of the crown ether from a folded, Pac-Man form with SmII to a twisted conformation with SmIII. The optical properties of [SmII(DB30C10)][BPh4]2 exhibit a strong temperature dependence and change from broad-band absorption features indicative of domination by 5d states to fine features characteristic of 4f → 4f transitions at low temperatures. Examination of the electronic structure of these complexes via ab initio wave function calculations (SO-CASSCF) shows that the ground state of SmII in [SmII(DB30C10)]2+ is a 4f6 state with low-lying 4f55d1 states, where the latter states have been lowered in energy by ∼12 000 cm-1 with respect to the free ion. The decacoordination of the SmII cation by the crown ether is responsible for this alteration in the energies of the excited state and demonstrates the ability to tune the electronic structure of SmII.

Intramolecular and lateral intermolecular hole transfer at the sensitized TiO2 interface.

Characterization of the redox properties of TiO2 interfaces sensitized to visible light by a series of cyclometalated ruthenium polypyridyl compounds containing both a terpyridyl ligand with three carboxylic acid/carboxylate or methyl ester groups for surface binding and a tridentate cyclometalated ligand with a conjugated triarylamine (NAr3) donor group is described. Spectroelectrochemical studies revealed non-Nernstian behavior with nonideality factors of 1.37 ± 0.08 for the Ru(III/II) couple and 1.15 ± 0.09 for the NAr3(•+/0) couple. Pulsed light excitation of the sensitized thin films resulted in rapid excited-state injection (k(inj) > 10(8) s(-1)) and in some cases hole transfer to NAr3 [TiO2(e(-))/Ru(III)-NAr3 → TiO2(e(-))/Ru(II)-NAr3(•+)]. The rate constants for charge recombination [TiO2(e(-))/Ru(III)-NAr3 → TiO2/Ru(II)-NAr3 or TiO2(e(-))/Ru(II)-NAr3(•+) → TiO2/Ru(II)-NAr3] were insensitive to the identity of the cyclometalated compound, while the open-circuit photovoltage was significantly larger for the compound with the highest quantum yield for hole transfer, behavior attributed to a larger dipole moment change (Δµ = 7.7 D). Visible-light excitation under conditions where the Ru(III) centers were oxidized resulted in injection into TiO2 [TiO2/Ru(III)-NAr3 + hν → TiO2(e(-))/Ru(III)-NAr3(•+)] followed by rapid back interfacial electron transfer to another oxidized compound that had not undergone excited-state injection [TiO2(e(-))/Ru(III)-NAr3 → TiO2/Ru(II)-NAr3]. The net effect was the photogeneration of equal numbers of fully reduced and fully oxidized compounds. Lateral intermolecular hole hopping (TiO2/Ru(II)-NAr3 + TiO2/Ru(III)-NAr3(•+) → 2TiO2/Ru(III)-NAr3) was observed spectroscopically and was modeled by Monte Carlo simulations that revealed an effective hole hopping rate of (130 ns)(-1).