The synthesis of hollow opening polyhedral cages has always been an attractive but challenging goal, especially with regard to inorganic polyhedral cages. Herein, we present a novel, 240-nuclearity giant polymolybdate cage prepared via hydrothermal synthesis. This cage is composed of 20 tripod-shaped [Mo6O22(SO3)] n−/[Mo6O21(SO4)] n− building blocks with three connected vertices and 30 cubane-type [Mo4O16] n− edge building blocks, featuring a rare, nearly regular pentagonal dodecahedron with a large inner cavity (diameter up to 1.8 nm) and 12 opening pentagonal windows. This is the highest nuclearity hollow opening dodecahedral cage reported to date. Importantly, this cage exhibits good stability in solution, as revealed by scanning transmission electron microscopy (STEM), TEM, UV–vis, and Raman spectra. In addition, the bulk sample of this compound exhibits an ultrahigh proton conductivity of 1.03 × 10–1 S cm–1 at 80 °C and 98% relative humidity, which is the highest among polyoxometalate-based crystalline proton conductors.

We describe a novel and simple mechanism for inducing ion concentration polarization (ICP) using a surface-patterned perm-selective nanoporous film like Nafion in single, open microchannels. Such a surface-patterned Nafion film can rapidly transport only cations from the anodic side to the cathodic side through the nanopore clusters so that it is possible to generate an ICP phenomenon near the Nafion film. In this work, we characterize transport phenomena and distributions of ion concentration under various electric fields near the Nafion film and show that single-channel based ICP (SC-ICP) is affected by Nafion film thicknesses, strengths of applied electric fields, and ionic strengths of buffer solutions. We also emphasize that SC-ICP devices have several advantages over previous dual-channel ICP (DC-ICP) devices: easy and simple fabrication processes, inherently leak-tight, simple experimental setup requiring only one pair of electrodes, stable and robust ICP induced rapidly, and low electrical resistances helping to avoid Joule heating, and membrane perm-selectivity breakdown but allowing as high bulk flow as an open, plain microchannel. As an example of applications, we demonstrate that SC-ICP devices not only have high potential in pre-concentrating proteins in massively parallel microchannels but also enable the concentration and lysis of bacterial cells simultaneously and continuously on a chip; therefore, proteins within the cells are extracted, separated from the concentrated cells and then pre-concentrated at a different location that is closer to the Nafion film. Hence, we believe that the SC-ICP devices have higher possibilities of being easily integrated with traditional microfluidic systems for analytical and biotechnological applications.

Many microfluidic devices have been utilizing ion concentration polarization (ICP) phenomena by using a permselective, nanoporous membrane with electric fields for a variety of preconcentration applications. However, numerical analyses on the ICP phenomena have not drawn sufficient attention, although they are an intriguing and interdisciplinary research area. In this work, we propose a 2-D model and present numerical simulation results on the ICP, which were obtained by solving three coupled governing equations: Nernst-Planck, Navier-Stokes, and Poisson. With improved boundary conditions and assumptions, we demonstrated that the simulation results not only are consistent with other experimental results but also make it possible to thoroughly understand the ICP phenomena. In addition, we demonstrated that the preconcentration of analytes can be simulated and quantified in terms of concentration enhancement factors (CEFs) that were related to many factors, such as ionic concentration distribution, electric fields, and flow fields including vortex flows across the membrane. Furthermore, we demonstrated that a high electrophoretic mobility (EPM) of counterions in the membrane plays the most important role in producing accurate simulation results while the effect of the charge density of the membrane is relatively insignificant. Hence, it is believed that the model and simulation results would provide good guidelines to better develop microfluidic preconcentration devices based on the ICP phenomena.

Microfluidic devices utilize ion concentration polarization (ICP) phenomena for a variety of applications, but a comprehensive understanding of the generation of ICP is still necessary. Recently, the emergence of a novel single channel ICP (SC-ICP) device has stimulated further research on the mechanism of ICP generation, so that we developed a 2-D model of an SC-ICP device that integrates a nanoporous membrane on the bottom surface of the channel, allowing bulk flow over the membrane. We solved a set of coupled governing equations with appropriate boundary conditions to explore ICP numerically. As a result, we not only showed that the simulation results held a strong qualitative agreement with experimental results, but also found the distribution of ion concentrations in the SC-ICP device that has never been reported in previous studies. We confirmed again that the electrophoretic mobility (EPM) of counterions in the membrane is the most dominant factor determining the generation and strength of ICP, whereas the charge density of the membrane was dominant to the ICP strength only when a high EPM value was assumed. From the viewpoint of practical applications, an SC-ICP device with a long membrane under low buffer strength showed enhanced performance in the preconcentration of charged molecules. Therefore, we believe that the simulation results could not only provide sharp insight into ICP phenomena but also predict and optimize the performance of SC-ICP devices in various microfluidic applications.

Gd(III) chelates are important T1-weighted contrast agents used in clinical magnetic resonance imaging (MRI), but their low longitudinal relaxivity (r1) results in limited imaging efficiency. In this work, we utilize...