Four novel transition metal-carborane photosensitisers were prepared by Sonogashira cross-coupling of 1-(4-ethynylbenzyl)-2-methyl-o-carborane (A-CB) with halogenated Ru(II)- or Ir(III)-phenanthroline complexes. The resulting boron-rich complexes with one (RuCB and IrCB) or two carborane cages (RuCB2 and IrCB2) were spectroscopically characterised, and their photophysical properties investigated. RuCB displayed the most attractive photophysical properties in solution (λem 635 nm, τT 2.53 μs, and φp 20.4 %).
Nanosecond time-resolved transient absorption studies were used to explore the 3MLCT nature of the triplet excited states, and the highest singlet oxygen quantum yields (ΦΔ) were obtained for the mono-carborane-phenanthroline complexes (RuCB: 52 % and IrCB: 25 %). None of the complexes produce dark toxicity in SKBR-3 cells after incubation under photodynamic therapy (PDT) conditions. Remarkably, mono-carboranes RuCB and IrCB were the best internalised by the SKBR-3 cells, demonstrating the first examples of tris-bidentate transition metal-carborane complexes acting as triplet photosensitisers for PDT with a high photoactivity; RuCB or IrCB killed ∼50 % of SKBR-3 cells at 10 μM after irradiation. Therefore, the high-boron content and the photoactive properties of these photosensitisers make them potential candidates as dual anti-cancer agents for PDT and Boron Neutron Capture Therapy (BNCT).
Bioactive materials for therapy and diagnosis
Ru(II) and Ir(III) phenanthroline-based photosensitisers bearing o-carborane: PDT agents with boron carriers for potential BNCT
Sylvia M. Draper, Robert Conway-Kenny, Albert Ferrer-Ugalde, Oriol Careta, Xiaoneng Cui, Jianzhang Zhao, Carme Nogues, Rosario Nunez and Justo Cabrera-González
Nanostructuring nanocarbons with IrOx yields to material coatings with large charge capacities for neural electrostimulation, and large reproducibility in time, that carbons do not exhibit. This work shows the contributions of carbon and the different nanostructures present, as well as the impact of functionalizing graphene with oxygen and nitrogen, and the effects of including conducting polymers within the hybrid materials. Different mammalian neural growth models differentiate the roles of the substrate material in absence and in presence of applied electric fields and address optimal electrodes for the future clinical applications.
Electrodeposited iridium oxide (K1.7IrO0.8 (OH)2.2 × 1.8 H2O; also called IrOx) is among the best substrates for neural growth, decreasing impedance and stimulating cell growth, when used as a connected electrode. Without direct contact, it has been proven to stimulate neurons through a bipolar mechanism related to the conducting character of the material in the presence of remote electric fields.
This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime.
A multitude of microparticles and nanoparticles is developed to improve the delivery of different small drugs and large biomolecules, which are subject to several hindering biological barriers that limit their optimal biodistribution and therapeutic effects. Here, a soft, reliable, and scalable method based on compressed CO2 is reported for obtaining nanoconjugates of recombinant human epidermal growth factor and nanovesicles called quatsomes, where the latter consists of cholesterol and cetyltrimethylammonium bromide.These nanoconjugates exhibit appropriate values of the major critical quality attributes of colloidal nanomedicines, such as controlled and narrow nanoscopic particle size distribution (which play important roles in determining their stability), drug loading, drug release, drug protection, targeting ability, and bioactivity.
The use of surgical meshes to reinforce damaged internal soft tissues has been instrumental for successful hernia surgery; a highly prevalent condition affecting yearly more than 20 million patients worldwide. Intraperitoneal adhesions between meshes and viscera are one of the most threatening complications, often implying reoperation or side effects such as chronic pain and bowel perforation.