RESUMO
Redox-active tetraoxolene ligands such as 1,4-dihydroxybenzoquinone provide access to a diversity of metal-organic architectures, many of which display interesting magnetic behavior and high electrical conductivity. Here, we take a closer look at how structure dictates physical properties in a series of 1D iron-tetraoxolene chains. Using a diphenyl-derivatized tetraoxolene ligand (H2Ph2dhbq), we show that the steric profile of the coordinating solvent controls whether linear or helical chains are exclusively formed. Despite similar ligand environments, only the helical chain displays temperature-dependent valence tautomerism, switching from (FeII)(Ph2dhbq2-) to (FeIII)(Ph2dhbq3Ë-) at temperatures below 203 K. The stabilization of ligand radicals leads to exceptionally strong magnetic exchange coupling (J = -230 ± 4 cm-1). Meanwhile, the linear chains are more amenable to oxidative doping, leading to Robin-Day class II/III mixed-valency and an increase in electrical conductivity by nearly three orders of magnitude. While previous studies have focused on the effects of changing metal and ligand identity, this work highlights how altering the metal-ligand connectivity can be a similarly powerful tool for tuning materials properties.
RESUMO
Recently introduced nanoscale electrokinetic phenomenon called ion concentration polarization (ICP) has been suffered from serious pH changes to the sample fluid. A number of studies have focused on the origin of pH changes and strategies for regulating it. Instead of avoiding pH changes, in this work, we tried to demonstrate new ways to utilize this inevitable pH change. First, one can obtain a well-defined pH gradient in proton-received microchannel by applying a fixed electric current through a proton exchange membrane. Furthermore, one can tune the pH gradient on demand by adjusting the proton mass transportation (i.e., adjusting electric current). Secondly, we demonstrated that the occurrence of ICP can be examined by sensing a surrounding pH of electrolyte solution. When pH > threshold pH, patterned pH-responsive hydrogel inside a straight microchannel acted as a nanojunction to block the microchannel, while it did as a microjunction when pH < threshold pH. In case of forming a nanojunction, electrical current significantly dropped compared to the case of a microjunction. The strategies that presented in this work would be a basis for useful engineering applications such as a localized pH stimulation to biomolecules using tunable pH gradient generation and portable pH sensor with pH-sensitive hydrogel.
RESUMO
Recently, the ion concentration polarization (ICP) phenomenon has been actively utilized for low abundance biomolecular preconcentration applications. Since ICP significantly rearranges the ion distribution near a permselective membrane, its detailed investigation should be conducted for developing efficient platforms. In particular, proton transport through the membrane critically affects the pH of sample solutions so that continuous monitoring or batch measurement of pH is the priority task to be carried out. Moreover, electrochemical reactions have been overlooked, even though an overpotential is applied to preconcentrate a sample under physiological conditions, and the electrodes are in direct contact with the sample biomolecules. In this work, we experimentally visualized and directly measured how the electrochemical reaction dominated the preconcentration efficiency using two types of electrode configurations; large exposed electrode area (LEEA) and small exposed electrode area (SEEA). Interestingly, significant pH variation was confirmed only in the case of SEEA. As a result, the BSA preconcentration was impeded within a short period in the case of SEEA, but loss-free preconcentration was achieved in the case of LEEA. Therefore, one should pay careful attention to the electrode design of electrokinetic operation, especially when pH-sensitive biomolecules are involved.
