pH Valve Based on Hydrophobicity Switching

pH switchable valves were constructed using nanoporous membranes, the surface of which was modified by mixtures of aminopropyl trimethoxy silane and butyl trimethoxy silane. The modified membranes are dry at neutral and basic conditions because of their hydrophobicity but open to flux of aqueous solutions at slightly acidic pH because of protonation of amino groups. The resulting high contrast between the open and the closed states and a high flux in the open state because of large pore size make the approach attractive in applications where pH switching is employed, for example, in drug delivery applications

pH Valve Based on Hydrophobicity Switching

pH switchable valves were constructed using nanoporous membranes, the surface of which was modified by mixtures of aminopropyl trimethoxy silane and butyl trimethoxy silane. The modified membranes are dry at neutral and basic conditions because of their hydrophobicity but open to flux of aqueous solutions at slightly acidic pH because of protonation of amino groups. The resulting high contrast between the open and the closed states and a high flux in the open state because of large pore size make the approach attractive in applications where pH switching is employed, for example, in drug delivery applications

pH Valve Based on Hydrophobicity Switching

pH switchable valves were constructed using nanoporous membranes, the surface of which was modified by mixtures of aminopropyl trimethoxy silane and butyl trimethoxy silane. The modified membranes are dry at neutral and basic conditions because of their hydrophobicity but open to flux of aqueous solutions at slightly acidic pH because of protonation of amino groups. The resulting high contrast between the open and the closed states and a high flux in the open state because of large pore size make the approach attractive in applications where pH switching is employed, for example, in drug delivery applications

Surface-Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

Surface-assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to an oxide surface in the atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of the gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to half of that for the collision rate

Voltage-Gated Hydrophobic Nanopores

Hydrophobicity is a fundamental property that is responsible for numerous physical and biophysical aspects of molecular interactions in water. Peculiar behavior is expected for water in the vicinity of hydrophobic structures, such as nanopores. Indeed, hydrophobic nanopores can be found in two distinct states, dry and wet, even though the latter is thermodynamically unstable. Transitions between these two states are kinetically hindered in long pores but can be much faster in shorter pores. As it is demonstrated for the first time in this paper, these transitions can be induced by applying a voltage across a membrane with a single hydrophobic nanopore. Such voltage-induced gating in single nanopores can be realized in a reversible manner through electrowetting of inner walls of the nanopores. The resulting I–V curves of such artificial hydrophobic nanopores mimic biological voltage-gated channels

Improved Characterization of Aqueous Single-Walled Carbon Nanotube Dispersions Using Dynamic Light Scattering and Analytical Centrifuge Methods

Aqueous dispersions of single-walled carbon nanotubes (SWCNTs) with a surfactant were studied by using a combination of differential sedimentation and dynamic light scattering methods. When applied to elongated particles like SWCNTs, the differential sedimentation method makes it possible to measure their diameters in dispersions, while the dynamic light scattering method allows to measure their lengths. Both methods have logarithmic dependence on the ratio between the length and diameter of the particles, and their simultaneous use improves the accuracy of measuring particles’ dimensions. It was shown that sonication of dispersions leads not only to unbundling of agglomerates into individual nanotubes but also to a decrease in their lengths and the appearance of new defects detectable in increasing the D/G ratio in the Raman spectra. Unbundling into individual nanotubes occurs after exposure to 1 kWh/L energy density, and the single nanotube diameter with SDBS is ca. 3.3 nm larger than that of the naked nanotubes. Conductivity of thin SWCNT films made out of individual nanotubes demonstrates a power law dependence with the exponent close to the theoretical one for rigid rods

Simple and Versatile Detection of Viruses Using Anodized Alumina Membranes

A simple sensor for viral particles based on ionic conductivity through anodized alumina membranes was demonstrated using MS2 bacteriophage as an example. A facile two-point measuring scheme is geared toward realization using a computer’s sound card input/output capabilities suitable for a fast and inexpensive point of care testing. The lowest detection concentration down to ∼7 pfu/mL and a large dynamic range up to ∼2000 pfu/mL were obtained due to physical optimization that included proper length and diameter for the pores, removing the oxide layer at the electrode, as well as the chemical optimization of covalent binding of antibodies to the pore’s walls

Ionic Conductance through Graphene: Assessing Its Applicability as a Proton Selective Membrane

Inspired by recent reports on possible proton conductance through graphene, we have investigated the behavior of pristine graphene and defect engineered graphene membranes for ionic conductance and selectivity with the goal of evaluating a possibility of its application as a proton selective membrane. The averaged conductance for pristine chemical vapor deposited (CVD) graphene at pH1 is ∼4 mS/cm2 but varies strongly due to contributions from the unavoidable defects in our CVD graphene. From the variations in the conductance with electrolyte strength and pH, we can conclude that pristine graphene is fairly selective and the conductance is mainly due to protons. Engineering of the defects with ion beam (He+, Ga+) irradiation and plasma (N2 and H2) treatment showed improved areal conductance with high proton selectivity mostly for He-ion beam and H2 plasma treatments, which agrees with primarily vacancy-free type of defects produced in these cases confirmed by Raman analysis

Low-Temperature NMR Studies of the Structure and Dynamics of a Novel Series of Acid−Base Complexes of HF with Collidine Exhibiting Scalar Couplings Across Hydrogen Bonds^†

The low-temperature 1H, 19F, and 15N NMR spectra of mixtures of collidine-15N (2,4,6-trimethylpyridine-15N, Col) with HF have been measured using CDF3/CDF2Cl as a solvent in the temperature range 94−170 K. Below 140 K, the slow proton and hydrogen bond exchange regime is reached where four hydrogen-bonded complexes between collidine and HF with the compositions 1:1, 2:3, 1:2, and 1:3 could be observed and assigned. For these complexes, chemical shifts and scalar coupling constants across the 19F1H19F and 19F1H15N hydrogen bridges have been measured which allowed us to determine the chemical composition of the complexes. The simplest complex, collidine hydrofluoride ColHF, is characterized at low temperatures by a structure intermediate between a molecular and a zwitterionic complex. Its NMR parameters depend strongly on temperature and the polarity of the solvent. The 2:3 complex [ColHFHCol]+[FHF]- is a contact ion pair. Collidinium hydrogen difluoride [ColH]+[FHF]- is an ionic salt exhibiting a strong hydrogen bond between collidinium and the [FHF]- anion. In this complex, the anion [FHF]- is subject to a fast reorientation rendering both fluorine atoms equivalent in the NMR time scale with an activation energy of about 5 kcal mol-1 for the reorientation. Finally, collidinium dihydrogen trifluoride [ColH]+[F(HF)2]- is an ionic pair exhibiting one FHN and two FHF hydrogen bonds. Together with the [F(HF)n]- clusters studied previously (Shenderovich et al., Phys. Chem. Chem. Phys. 2002, 4, 5488), the new complexes represent an interesting model system where the evolution of scalar couplings between the heavy atoms and between the proton and the heavy atoms of hydrogen bonds can be studied. As in the related FHF case, we observe also for the FHN case a sign change of the coupling constant 1JFH when the F···H distance is increased and the proton shifted to nitrogen. When the sign change occurs, that is, 1JFH = 0, the heavy atom coupling constant 2JFN remains very large, of the order of 95 Hz. Using the valence bond order model and hydrogen bond correlations, we describe the dependence of the hydrogen bond coupling constants, of hydrogen bond chemical shifts, and of some H/D isotope effects on the latter as a function of the hydrogen bond geometries