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.
In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region. Thus, within the same junction it is possible to switch between Marcus and inverted Marcus regimes by changing the bias polarity. Consequently, the current only decreases with decreasing temperature at negative bias when hopping is “frozen out,” but not at positive bias resulting in a 30-fold increase in the molecular rectification efficiency. These results indicate that the charge transport in the inverted Marcus region is readily accessible in junctions with redox molecules in the weak coupling regime and control over different hopping regimes can be used to improve junction performance.
Bioactive materials for therapy and diagnosis
Bias-Polarity-Dependent Direct and Inverted Marcus Charge Transport Affecting Rectification in a Redox-Active Molecular Junction
Yingmei Han, Cameron Nickle, Maria Serena Maglione, Senthil Kumar Karuppannan, Javier Casado-Montenegro, Dong-Chen Qi, Xiaoping Chen, Anton Tadich, Bruce Cowie, Marta Mas-Torrent, Concepció Rovira, Jérôme Cornil, Jaume Veciana, Enrique del Barco, Christian A. Nijhuis
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.
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 %).
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.