Triazol-Methanaminium-Pillar[5]arene-Functionalized Single Nanochannel for Quantitative Analysis of Pyrophosphate in Water.

Inorganic pyrophosphate (PPi) is an important biological functional anion and plays crucial roles in life science, environmental science, medicine, and chemical process. Quantification of PPi in water has far-reaching significance for life exploration, disease diagnosis, and water pollution control. The label-free quantitative detection of PPi anions with a nanofluidic sensing device based on a conical single nanochannel is demonstrated. The channel surface is functionalized with a synthetic PPi receptor, triazol-methanaminium-functionalized pillar[5]arene (TAMAP5), using carbodiimide coupling chemistry. Due to the specific binding between TAMAP5 and PPi, the functionalized nanochannel can discriminate PPi from other inorganic anions with high selectivity through ionic current recording, even in the presence of various interfering anions. The current response exhibits a linear correlation with PPi concentration in the range from 1 × 10-7 to 1 × 10-4 M with a limit of detection of 6.8 × 10-7 M. A spike-and-recovery analysis of PPi in East Lake water samples indicates that the proposed nanofluidic sensor has the ability to quantitate micromolar concentrations of PPi in environmental water samples.

Efficient Chiral Nanosenor Based on Tip-Modified Nanochannels.

Enantiomers of various drug molecules have a specific effect on living organisms. Accordingly, developing a sample method for the efficient and rapid recognition of chiral drug enantiomers is of great industrial value and physiological significance. Here, inspired by the structure of ion channels in living organisms, we developed a chiral nanosensor based on an artificial tip-modified nanochannel system that allows efficient selective recognition of chiral drugs. In this system, l-alanine-pillar[5]arenes as selective receptors were introduced on the tip side of conical nanochannels to form an enantioselective "gate". The selective coefficient of our system toward R-propranolol is 4.96, which is higher than the traditional fully modified nanochannels in this work.

Etched ion-track membranes as tailored separators in Li-S batteries.

Lithium-sulfur (Li-S) batteries are considered a promising next generation alternative to lithium-ion batteries for energy storage systems due to its high energy density. However, several challenges, such as the polysulfide redox shuttle causing self-discharge of the battery, remain unresolved. In this paper, we explore the use of polymer etched ion-track membranes as separators in Li-S batteries to mitigate the redox shuttle effect. Compared to commercial separators, their unique advantages lie in their very narrow pore size distribution, and the possibility to tailor and optimize the density, geometry, and diameter of the nanopores in an independent manner. Various polyethylene terephthalate membranes with diameters between 22 and 198 nm and different porosities were successfully integrated into Li-S coin cells. The reported coulombic efficiency of up to 97% with minor reduction in capacity opens a pathway to potentially address the polysulfide redox shuttle in Li-S batteries using tailored membranes.

Ion track etching of polycarbonate membranes monitored by in situ small angle X-ray scattering.

In situ small angle X-ray scattering (SAXS) measurements of ion track etching in polycarbonate foils are used to directly monitor the selective dissolution of ion tracks with high precision, including the early stages of etching. Detailed information about the track etching kinetics and size, shape, and size distribution of an ensemble of nanopores is obtained. Time resolved measurements as a function of temperature and etchant concentration show that the pore radius increases almost linearly with time for all conditions and the etching process can be described by an Arrhenius law. The radial etching shows a power law dependency on the etchant concentration. An increase in the etch rate with increasing temperature or concentration of the etchant reduces the penetration of the etchant into the polymer but does not affect the pore size distribution. The in situ measurements provide an estimate for the track etch rate, which is found to be approximately three orders of magnitude higher than the radial etch rate. The measurement methodology enables new experiments studying membrane fabrication and performance in liquid environments.

Highly Sensitive Biosensing with Solid-State Nanopores Displaying Enzymatically Reconfigurable Rectification Properties.

Molecular design of biosensors based on enzymatic processes taking place in nanofluidic elements is receiving increasing attention by the scientific community. In this work, we describe the construction of novel ultrasensitive enzymatic nanopore biosensors employing "reactive signal amplifiers" as key elements coupled to the transduction mechanism. The proposed framework offers innovative design concepts not only to amplify the detected ionic signal and develop ultrasensitive nanopore-based sensors but also to construct nanofluidic diodes displaying specific chemo-reversible rectification properties. The integrated approach is demonstrated by electrostatically assembling poly(allylamine) on the anionic pore walls followed by the assembly of urease. We show that the cationic weak polyelectrolyte acts as a "reactive signal amplifier" in the presence of local pH changes induced by the enzymatic reaction. These bioinduced variations in proton concentration ultimately alter the protonation degree of the polyamine resulting in amplifiable, controlled, and reproducible changes in the surface charge of the pore walls, and consequently on the generated ionic signals. The "iontronic" response of the as-obtained devices is fully reversible, and nanopores are reused and assayed with different urea concentrations, thus ensuring reliable design. The limit of detection (LOD) was 1 nM. To the best of our knowledge, this value is the lowest LOD reported to date for enzymatic urea detection. In this context, we envision that this approach based on the use of "reactive signal amplifiers" into solid-state nanochannels will provide new alternatives for the molecular design of highly sensitive nanopore biosensors as well as (bio)chemically addressable nanofluidic elements.

Phosphate-Responsive Biomimetic Nanofluidic Diodes Regulated by Polyamine-Phosphate Interactions: Insights into Their Functional Behavior from Theory and Experiment.

There is currently high interest in developing nanofluidic devices whose iontronic output is defined by biological interactions. The fabrication of a phosphate responsive nanofluidic diode by using the biological relevant amine-phosphate interactions is shown. The fabrication procedure includes the modification of a track-etched asymmetric (conical) nanochannel with polyallylamine (PAH) by electrostatic self-assembly. PAH is the arcaetypical model of polyamine and it is further used to address the nanochannels with phosphate responsivity. In order to explore the influence that phosphate in solution has in the conductance of the modified nanochannels, current-voltage measurements using different concentrations of phosphates are performed. Furthermore, to have a complete physicochemical understanding of the system, experimental data is analyzed using a continuous model based on Poison-Nernst-Planck equations and compared with results obtained from stochastic Monte Carlo simulations.

Osmotic Effects in Track-Etched Nanopores.

Asymmetrically etched ion-track membranes attract great interest for both fundamental and technical reasons because of a large variety of applications. So far, conductometric measurements during track etching provide only limited information about the complicated asymmetric etching process. In this paper, monitoring of osmotic phenomena is used to elucidate the initial phase of nanopore formation. It is shown that strong alkaline solutions generate a considerable osmotic flow of water through newborn conical pores. The interplay between diffusion and convection in the pore channel results in a substantially nonlinear alkali concentration gradient and a rapid change in the pore geometry after breakthrough. Similar phenomena are observed in experiments with cylindrical track-etched pores of 15-30 nm in radius. A theoretical description of the diffusion-convection processes in the pores is provided.

Proton-Gated Rectification Regimes in Nanofluidic Diodes Switched by Chemical Effectors.

During the last decade, nanofluidic devices based on solid-state nanopores and nanochannels have come into scene in materials science and will not leave anytime soon. One of the main reasons for this is the excellent control over ionic transport exerted by such devices that promises further important advances when integrated into more complex molecular devices. As a result, pH, temperature, and voltage-regulated devices have been obtained. However, nowadays, there is still a necessity for molecule-driven nanofluidic devices. Here, a sugar-regulated pH-responsive nanofluidic diode is presented obtained by surface modification of conical polycarbonate nanochannels with electropolymerized 3-aminophenylboronic acid. Control over the ionic transport has been achieved by a successful decoration of asymmetric nanochannels with integrated molecular systems. The as-synthesized boronate-appended zwitterionic polymer exhibits an acid-base equilibrium that depends on the concentration of sugar, which ultimately acts as a chemical effector setting different pH-dependent rectification regimes. As a result, the same nanodevice can perform completely different proton-regulated nanofluidic operations, i.e., anion-driven rectification, cation-driven rectification, and no rectification, by simply varying the concentration of fructose in the electrolyte solution.

Erratum: Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling [Phys. Rev. Lett. 120, 015501 (2018)].

This corrects the article DOI: 10.1103/PhysRevLett.120.015501.

Shrinking of Rapidly Evaporating Water Microdroplets Reveals their Extreme Supercooling.

The fast evaporative cooling of micrometer-sized water droplets in a vacuum offers the appealing possibility to investigate supercooled water-below the melting point but still a liquid-at temperatures far beyond the state of the art. However, it is challenging to obtain a reliable value of the droplet temperature under such extreme experimental conditions. Here, the observation of morphology-dependent resonances in the Raman scattering from a train of perfectly uniform water droplets allows us to measure the variation in droplet size resulting from evaporative mass losses with an absolute precision of better than 0.2%. This finding proves crucial to an unambiguous determination of the droplet temperature. In particular, we find that a fraction of water droplets with an initial diameter of 6379±12 nm remain liquid down to 230.6±0.6 K. Our results question temperature estimates reported recently for larger supercooled water droplets and provide valuable information on the hydrogen-bond network in liquid water in the hard-to-access deeply supercooled regime.

Radiation-induced disorder in compressed lanthanide zirconates.

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln2Zr2O7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm2Zr2O7 and Nd2Zr2O7. For irradiated Er2Zr2O7, which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Exploring the Electronic Structure and Chemical Homogeneity of Individual Bi2Te3 Nanowires by Nano-Angle-Resolved Photoemission Spectroscopy.

Due to their high surface-to-volume ratio, cylindrical Bi2Te3 nanowires are employed as model systems to investigate the chemistry and the unique conductive surface states of topological insulator nanomaterials. We report on nanoangle-resolved photoemission spectroscopy (nano-ARPES) characterization of individual cylindrical Bi2Te3 nanowires with a diameter of 100 nm. The nanowires are synthesized by electrochemical deposition inside channels of ion-track etched polymer membranes. Core level spectra recorded with submicron resolution indicate a homogeneous chemical composition along individual nanowires, while nano-ARPES intensity maps reveal the valence band structure at the single nanowire level. First-principles electronic structure calculations for chosen crystallographic orientations are in good agreement with those revealed by nano-ARPES. The successful application of nano-ARPES on single one-dimensional nanostructures constitutes a new avenue to achieve a better understanding of the electronic structure of topological insulator nanomaterials.

The Influence of Divalent Anions on the Rectification Properties of Nanofluidic Diodes: Insights from Experiments and Theoretical Simulations.

During the last decade, the possibility of generating synthetic nanoarchitectures with functionalities comparable to biological entities has sparked the interest of the scientific community related to diverse research fields. In this context, gaining fundamental understanding of the central features that determine the rectifying characteristics of the conical nanopores is of mandatory importance. In this work, we analyze the influence of mono- and divalent salts in the ionic current transported by asymmetric nanopores and focus on the delicate interplay between ion exclusion and charge screening effects that govern the functional response of the nanofluidic device. Experiments were performed using KCl and K2 SO4 as representative species of singly and doubly charged species. Results showed that higher currents and rectification efficiencies are achieved by doubly charged salts. In order to understand the physicochemical processes underlying these effects simulations using the Poisson-Nernst-Planck formalism were performed. We consider that our theoretical and experimental account of the effect of divalent anions in the functional response of nanofluidic diodes provides further insights into the critical role of electrostatic interactions (ion exclusion versus charge screening effects) in presetting the ionic selectivity to anions as well as the observed rectification properties of these chemical nanodevices.

Shedding light on the mechanism of asymmetric track etching: an interplay between latent track structure, etchant diffusion and osmotic flow.

The method of producing single track-etched conical nanopores has received considerable attention and found many applications in diverse fields such as biosensing, nanofluidics, information processing and others. The performance of an asymmetric nanopore is largely determined by its geometry, especially by the size and shape of its tip. In this paper we reconstruct the profiles of so-called conical pores fabricated by asymmetric chemical etching of ion tracks in polymer foil. Conductometric measurements during etching and field emission scanning electron microscopy examinations of the resulting pores were employed in order to determine the pore geometry. We demonstrate that the pore constriction geometry evolves through a variety of configurations with advancing time after breakthrough. While immediately after breakthrough the pore tips are trumpet-shaped, further etching is strongly affected by osmotic effects which eventually lead to bullet-shaped pore tips. We evidence that the osmotic flow appearing during asymmetric track etching has a determinative effect on pore formation. A convection-diffusion model is presented that semi-quantitatively explains the effect of osmotic processes under asymmetric track etching conditions. In addition, a phenomenon of reagent contaminant precipitation in nanopores is reported and discussed.

Polydopamine meets solid-state nanopores: a bioinspired integrative surface chemistry approach to tailor the functional properties of nanofluidic diodes.

The ability to modulate the surface chemical characteristics of solid-state nanopores is of great interest as it provides the means to control the macroscopic response of nanofluidic devices. For instance, controlling surface charge and polarity of the pore walls is one of the most important applications of surface modification that is very relevant to attain accurate control over the transport of ions through the nanofluidic architecture. In this work, we describe a new integrative chemical approach to fabricate nanofluidic diodes based on the self-polymerization of dopamine (PDOPA) on asymmetric track-etched nanopores. Our results demonstrate that PDOPA coating is not only a simple and effective method to modify the inner surface of polymer nanopores fully compatible with the fabrication of nanofluidic devices but also a versatile platform for further integration of more complex molecules through different covalent chemistries and self-assembly processes. We adjusted the chemical modification strategy to obtain various configurations of the pore surface: (i) PDOPA layer was used as primer, precursor, or even responsive functional coating; (ii) PDOPA layer was used as a platform for anchoring chemical functions via the Michael addition reaction; and (iii) PDOPA was used as a reactive layer inducing the metallization of the pore walls through the in situ reduction of metallic precursors present in solution. We believe that the transversal concept of integrative surface chemistry offered by polydopamine in combination with the remarkable physical characteristics of asymmetric nanopores constitutes a new framework to design multifunctional nanofluidic devices employing soft chemistry-based nanofunctionalization techniques.

Nanofluidic Diodes with Dynamic Rectification Properties Stemming from Reversible Electrochemical Conversions in Conducting Polymers.

The use of solid state nanochannels as nanofluidic diodes is currently a topic of large interest in nanotechnology. Particularly, there is a focus in the development of nanochannels with surface functionalities that make them responsive to multiple environmental variables. Here, we present for the first time the construction of electrochemical potential- and pH-responsive nanofluidic diodes using a novel approach based on a controlled electrochemical polymerization of aniline on gold-coated polycarbonate asymmetric nanochannels. The polyaniline-modified nanochannels showed three different levels of reversible ionic rectification corresponding to the degrees of oxidation of the conducting polymer. Our results demonstrate that this strategy enables an accurate and reversible control of the rectification properties due to the well-defined and predictable electrochemical conversion of charged species generated on the pore walls. We envision that these results will create novel avenues to fabricate electrochemically modulated nanofluidic diodes using conducting polymers integrated into single conical nanopores.

TiO2, SiO2, and Al2O3 coated nanopores and nanotubes produced by ALD in etched ion-track membranes for transport measurements.

Low-temperature atomic layer deposition (ALD) of TiO2, SiO2, and Al2O3 was applied to modify the surface and to tailor the diameter of nanochannels in etched ion-track polycarbonate membranes. The homogeneity, conformity, and composition of the coating inside the nanochannels are investigated for different channel diameters (18-55 nm) and film thicknesses (5-22 nm). Small angle x-ray scattering before and after ALD demonstrates conformal coating along the full channel length. X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy provide evidence of nearly stoichiometric composition of the different coatings. By wet-chemical methods, the ALD-deposited film is released from the supporting polymer templates providing 30 µm long self-supporting nanotubes with walls as thin as 5 nm. Electrolytic ion-conductivity measurements provide proof-of-concept that combining ALD coating with ion-track nanotechnology offers promising perspectives for single-pore applications by controlled shrinking of an oversized pore to a preferred smaller diameter and fine-tuning of the chemical and physical nature of the inner channel surface.

Nanoscale core-shell structure and recrystallization of swift heavy ion tracks in SrTiO3.

It is widely accepted that the interaction of swift heavy ions with many complex oxides is predominantly governed by the electronic energy loss that gives rise to nanoscale amorphous ion tracks along the penetration direction. The question of how electronic excitation and electron-phonon coupling affect the atomic system through defect production, recrystallization, and strain effects has not yet been fully clarified. To advance the knowledge of the atomic structure of ion tracks, we irradiated single crystalline SrTiO3 with 629 MeV Xe ions and performed comprehensive electron microscopy investigations complemented by molecular dynamics simulations. This study shows discontinuous ion-track formation along the ion penetration path, comprising an amorphous core and a surrounding few monolayer thick shell of strained/defective crystalline SrTiO3. Using machine-learning-aided analysis of atomic-scale images, we demonstrate the presence of 4-8% strain in the disordered region interfacing with the amorphous core in the initially formed ion tracks. Under constant exposure of the electron beam during imaging, the amorphous part of the ion tracks readily recrystallizes radially inwards from the crystalline-amorphous interface under the constant electron-beam irradiation during the imaging. Cation strain in the amorphous region is observed to be significantly recovered, while the oxygen sublattice remains strained even under the electron irradiation due to the present oxygen vacancies. The molecular dynamics simulations support this observation and suggest that local transient heating and annealing facilitate recrystallization process of the amorphous phase and drive Sr and Ti sublattices to rearrange. In contrast, the annealing of O atoms is difficult, thus leaving a remnant of oxygen vacancies and strain even after recrystallization. This work provides insights for creating and transforming novel interfaces and nanostructures for future functional applications.

Thinning of Poly(methyl methacrylate) and Poly(vinyl chloride) Thin Films Induced by High-Energy Ions of Different Stopping Powers.

Ion bombardment is an important tool of materials processing, but usually leads to erosion of the surface and significant thickness reductions when thin layers are used. The growing use of polymer thin films in a variety of applications, from coatings and membranes to biomedical and electronic devices, calls for a deeper understanding of the thinning process induced by energetic ions espe-cially for very thin films. Here, thinning and surface morphology changes induced by high-energy ion bombardment in PMMA and PVC thin films were investigated, focusing on the role of the initial thickness of the films and the stopping power of the ions. We used thin films with initial thicknesses varying from 13 to 800 nm, and light and heavy ions as projectiles in the energy range of 2-2000 MeV, where the electronic stopping dominates. Thickness reductions as a function of fluence were monitored and thinning cross sections were extracted from curves. A supralinear scaling between the thinning cross sections and the electronic stopping power of the beams was observed, with a much enhanced thinning efficiency for the swift heavy ions. The scaling with the stopping power dE/dx is almost independent of the initial thickness of the films. At intermediate and large fluences, changes in the physicochemical properties of the irradiated polymers may modulate and decelerate the thinning process of the remaining film. The importance of this secondary process depends on the stopping power and the balance between erosion and the chemical transformations induced by the beam. We also observe a trend for the thinning efficiency to become larger in very thin films. Depending on the type of beam and polymer, this effect is more or less pronounced. PMMA films irradiated with 2 MeV H+ show the most systematic correlation between initial thickness and thinning cross sections, while in PVC films the initial thickness plays a minor role for all investigated beams.

Three-dimensional free-standing gold nanowire networks as a platform for catalytic applications.

We report the catalytic performance of networks of highly interconnected Au nanowires with diameters tailored between 80 and 170 nm. The networks were synthesized by electrodeposition in etched ion-track polymer templates, and the synthesis conditions were developed for optimal wire crystallinity and network homogeneity. The nanowire networks were self-supporting and could be easily handled as electrodes in electrochemical cells or other devices. The electrochemically active surface area of the networks increased systematically with increasing the wire diameter. They showed a very stable performance during 200 CV cycles of methanol oxidation reactions, with the peak current density reaching up to 200 times higher than that of a flat reference electrode, with only a 5% drop in the peak current density. The Au nanowire networks proved to be excellent model systems for investigation of the performance of porous catalysts and very promising nanosystems for application in direct alcohol fuel cell catalysts.