Polymeric liquids in mesoporous photonic structures: From precursor film spreading to imbibition dynamics at the nanoscale.

Polymers are known to wet nanopores with high surface energy through an atomically thin precursor film followed by slower capillary filling. We present here light interference spectroscopy using a mesoporous membrane-based chip that allows us to observe the dynamics of these phenomena in situ down to the sub-nanometer scale at milli- to microsecond temporal resolution. The device consists of a mesoporous silicon film (average pore size 6 nm) with an integrated photonic crystal, which permits to simultaneously measure the phase shift of thin film interference and the resonance of the photonic crystal upon imbibition. For a styrene dimer, we find a flat fluid front without a precursor film, while the pentamer forms an expanding molecular thin film moving in front of the menisci of the capillary filling. These different behaviors are attributed to a significantly faster pore-surface diffusion compared to the imbibition dynamics for the pentamer and vice versa for the dimer. In addition, both oligomers exhibit anomalously slow imbibition dynamics, which could be explained by apparent viscosities of six and eleven times the bulk value, respectively. However, a more consistent description of the dynamics is achieved by a constriction model that emphasizes the increasing importance of local undulations in the pore radius with the molecular size and includes a sub-nanometer hydrodynamic dead, immobile zone at the pore wall but otherwise uses bulk fluid parameters. Overall, our study illustrates that interferometric, opto-fluidic experiments with mesoporous media allow for a remarkably detailed exploration of the nano-rheology of polymeric liquids.

Increased Readiness for Water Splitting: NiO-Induced Weakening of Bonds in Water Molecules as Possible Cause of Ultra-Low Oxygen Evolution Potential.

The development of non-precious metal-based electrodes that actively and stably support the oxygen evolution reaction (OER) in water electrolysis systems remains a challenge, especially at low pH levels. The recently published study has conclusively shown that the addition of haematite to H2 SO4 is a highly effective method of significantly reducing oxygen evolution overpotential and extending anode life. The far superior result is achieved by concentrating oxygen evolution centres on the oxide particles rather than on the electrode. However, unsatisfactory Faradaic efficiencies of the OER and hydrogen evolution reaction (HER) parts as well as the required high haematite load impede applicability and upscaling of this process. Here it is shown that the same performance is achieved with three times less metal oxide powder if NiO/H2 SO4 suspensions are used along with stainless steel anodes. The reason for the enormous improvement in OER performance by adding NiO to the electrolyte is the weakening of the intramolecular O─H bond in the water molecules, which is under the direct influence of the nickel oxide suspended in the electrolyte. The manipulation of bonds in water molecules to increase the tendency of the water to split is a ground-breaking development, as shown in this first example.

High-Temperature Melt Stamping of Polymers Using Polymer/Nanoporous Gold Composite Stamps.

Parallel lithographic deposition of polymers onto counterpart substrates is a widely applied surface manufacturing operation. However, polymers may only be soluble in organic solvents or are insoluble at all. Solvent evaporation during stamping may trigger hardly controllable capillarity-driven flow processes or phase separation, and polymer solutions may spread on the counterpart substrates. Solvent-free stamping of melts prevents these drawbacks. Here, a stamp design for the deposition of melts is devised, which intrinsically circumvents ink depletion. The stamps' topographically patterned contact surfaces with protruding contact elements contacting the counterpart substrates consist of a nanoporous gold layer with a thickness of a few micrometers. The nanoporous gold layer is attached to a molten polymer layer, which is support for the nanoporous gold layer and ink reservoir at the same time. The nanoporous gold layer in turn stabilizes the topography of the stamps' contact surfaces. As examples, arrays of submicron microdots of polystyrene and poly(vinylidenefluoride-trifluoroethylene) (PVDF-TrFE) are manufactured. The P(VDF-TrFE) microdots are partially crystalline, ferroelectric, and can be locally poled. It is envisioned that the methodology reported here can be automatized and may be extended to functional low-molecular-mass compounds, such as active pharmaceutical ingredients.

Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores.

We report the imbibition and adsorption kinetics of a series of symmetric linear/star cis-1,4-polyisoprene blends within the long channels of self-ordered nanoporous anodic aluminum oxide (abbreviated: AAO). Using in situ nanodielectric spectroscopy, we followed the evolution of the longest chain modes in the blends with a judicious selection of molar masses for the constituent components. We demonstrated differences in the imbibition kinetics of linear and star components based on the relative viscosities (e.g., polymers with lower zero-shear viscosity penetrated first the nanopores). Following the complete imbibition of the pores, the adsorption time, τads, of each component was evaluated from the reduction in the dielectric strength of the respective chain modes. In the majority of blends, both components exhibited slower adsorption kinetics with respect to the homopolymers. The only exception was the case of entangled stars mixed with shorter linear chains, the latter acting as a diluent for the star component. This gives rise to what is known as topology sorting, e.g., the separation of linear/star blend components in the absence of solvent. Moreover, a simple relation (τads ∼ 10 × tpeak; tpeak is the time needed for the complete filling of pores) was found for linear polymers and stars. This suggested that the characteristic timescale of imbibition (tpeak) governs the adsorption process of polymers. It further implied the possibility of predicting the adsorption times of high molar mass polymers of various architectures by the shorter imbibition times.

Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores.

The conductivity of ionic liquids (ILs) in nanopores is essential when considering their application as materials for energy. However, no consensus has been reached about the influence of confinement on the mobility of the ions. A series of ILs bearing the same cation, 1-butyl-3-methylimidazolium ([BMIM]+), and six different anions ([Cl]-, [Br]-, [I]-, [BF4]-, [PF6]-, and [TFSI]-) with radii from 0.168 to 0.326 nm were investigated with respect to their self-assembly, the thermodynamics, and the ionic conductivity in the bulk, during flow and under confinement in cylindrical nanopores with sizes in the range from 400 to 25 nm. In the bulk, the [BMIM]+[X]- exhibits weak ordering as a result of cation-anion correlations (charge alteration peak), and nanophase separation of polar/apolar groups. Liquid-to-glass temperatures were found to differ by ∼50 K, their viscosities by a factor of ∼270, and their conductivities by a factor of 24 (all at a temperature of 303 K). Electrostatic interactions were largely responsible for variations in the glass temperature, the viscosity, and the conductivity. Confined ILs behave differently from the bulk. The majority of ILs in the bulk were prone to crystallization during heating but were unable to crystallize in the smaller pores. Changes in dc-conductivity were used as markers of the phase state. This allowed the construction of the effective phase diagrams under confinement. The ILs penetrate the pores with an effective viscosity of the order of their viscosity in their bulk state. However, within the pores the dc-conductivity was reduced relative to bulk, indicating the immobilization of ions at the pore walls. Hydrophobization of the pore walls by hexamethyldisilazane could partially restore the conductivity. ILs are model systems where the phase state and ion mobility can be controlled by confinement.

When crystals flow.

Semicrystalline polymers are solids that are supposed to flow only above their melting temperature. By using confinement within nanoscopic cylindrical pores, we show that a semicrystalline polymer can flow at temperatures below the melting point with a viscosity intermediate to the melt and crystal states. During this process, the capillary force is strong and drags the polymer chains in the pores without melting the crystal. The unexpected enhancement in flow, while preserving the polymer crystallites, is of importance in the design of polymer processing conditions applicable at low temperatures, e.g., cold drawn polymers such as polytetrafluoroethylene, self-healing, and in nanoconfined donor/acceptor polymers used in organic electronics.

Click-Functionalization of Silanized Carbon Nanotubes: From Inorganic Heterostructures to Biosensing Nanohybrids.

Here we present an approach to functionalize silanized single-walled carbon nanotubes (SWNTs) through copper-free click chemistry for the assembly of inorganic and biological nanohybrids. The nanotube functionalization route involves silanization and strain-promoted azide-alkyne cycloaddition reactions (SPACC). This was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and Fourier transform infra-red spectroscopy. Silane-azide-functionalized SWNTs were immobilized from solution onto patterned substrates through dielectrophoresis (DEP). We demonstrate the general applicability of our strategy for the functionalization of SWNTs with metal nanoparticles (gold nanoparticles), fluorescent dyes (Alexa Fluor 647) and biomolecules (aptamers). In this regard, dopamine-binding aptamers were conjugated to the functionalized SWNTs to perform real-time detection of dopamine at different concentrations. Additionally, the chemical route is shown to selectively functionalize individual nanotubes grown on the surface of silicon substrates, contributing towards future nano electronic device applications.

Dispersible SnO2 :Sb and TiO2 Nanocrystals After Calcination at High Temperature.

High-temperature treatment of functional nanomaterials, through postsynthesis calcination, often represents an important step to unlock their full potential. However, such calcination steps usually severely limit the preparation of colloidal solutions of the nanoparticles due to the formation of sintered agglomerates. Herein, a simple route is reported to obtain colloidal solutions of calcined n-conductive antimony doped tin oxide (ATO) as well as titanium dioxide (TiO2 ) nanoparticles without the need for additional sacrificial materials. This is achieved by making use of the reduced contact between individual nanoparticles when they are assembled into aerogels. Following the calcination of the aerogels at 500 °C, redispersion of the nanoparticles into stable colloidal solutions with various solvents can be achieved. Although a slight degree of sintering is inevitable, the size of the resulting aggregates in solution is still remarkably small with values below 30 nm.

Biofunctional Nanodot Arrays in Living Cells Uncover Synergistic Co-Condensation of Wnt Signalodroplets.

Qualitative and quantitative analysis of transient signaling platforms in the plasma membrane has remained a key experimental challenge. Here, biofunctional nanodot arrays (bNDAs) are developed to spatially control dimerization and clustering of cell surface receptors at the nanoscale. High-contrast bNDAs with spot diameters of ≈300 nm are obtained by capillary nanostamping of bovine serum albumin bioconjugates, which are subsequently biofunctionalized by reaction with tandem anti-green fluorescence protein (GFP) clamp fusions. Spatially controlled assembly of active Wnt signalosomes is achieved at the nanoscale in the plasma membrane of live cells by capturing the co-receptor Lrp6 into bNDAs via an extracellular GFP tag. Strikingly, co-recruitment is observed of co-receptor Frizzled-8 as well as the cytosolic scaffold proteins Axin-1 and Disheveled-2 into Lrp6 nanodots in the absence of ligand. Density variation and the high dynamics of effector proteins uncover highly cooperative liquid-liquid phase separation (LLPS)-driven assembly of Wnt "signalodroplets" at the plasma membrane, pinpointing the synergistic effects of LLPS for Wnt signaling amplification. These insights highlight the potential of bNDAs for systematically interrogating nanoscale signaling platforms and condensation at the plasma membrane of live cells.

Reactive Additive Capillary Stamping with Double Network Hydrogel-Derived Aerogel Stamps under Solvothermal Conditions.

Integration of solvothermal reaction products into complex thin-layer architectures is frequently achieved by combinations of layer transfer and subtractive lithography, whereas direct additive substrate patterning with solvothermal reaction products has remained challenging. We report reactive additive capillary stamping under solvothermal conditions as a parallel contact-lithographic access to patterns of solvothermal reaction products in thin-layer configurations. To this end, corresponding precursor inks are infiltrated into mechanically robust mesoporous aerogel stamps derived from double-network hydrogels. The stamp is then brought into contact with a substrate to be patterned under solvothermal reaction conditions inside an autoclave. The precursor ink forms liquid bridges between the topographic surface pattern of the stamp and the substrate. Evaporation-driven enrichment of the precursors in these liquid bridges, along with their liquid-bridge-guided conversion into the solvothermal reaction products, yields large-area submicron patterns of the solvothermal reaction products replicating the stamp topography. For example, we prepared thin hybrid films, which contained ordered monolayers of superparamagnetic submicron nickel ferrite dots prepared by solvothermal capillary stamping surrounded by nickel electrodeposited in a second orthogonal substrate functionalization step. The submicron nickel ferrite dots acted as a magnetic hardener, halving the remanence of the ferromagnetic nickel layer. In this way, thin-layer electromechanical systems, transformers, and positioning systems may be customized.

Melting Temperature Depression and Phase Transitions of Nitrate-Based Molten Salts in Nanoconfinement.

Hybrids of nitrate-based molten salts (KNO3, NaNO3, and Solar Salt) and anodic aluminum oxide (AAO) with various pore sizes (between 25 and 380 nm) were designed for concentrated solar power (CSP) plants to achieve low melting point (<200 °C) and high thermal conductivity (>1 W m-1 K-1). AAO pore surfaces were passivated with octadecyl phosphonic acid (ODPA), and the results were compared with as-anodized AAO. The change in phase transition temperatures and melting temperatures of salts was investigated as a function of pore diameter. Melting temperatures decreased for all salts inside AAO with different pore sizes while the highest melting temperature decrease (ΔT = 173 ± 2 °C) was observed for KNO3 filled in AAO with a pore diameter of 380 nm. Another nanoconfinement effect was observed in the crystal phases of the salts. The ferroelectric phase of KNO3 (γ-phase) formed at room temperature for KNO3/AAO hybrids with pore size larger than 35 nm. Thermal conductivity values of molten salt (MS)/AAO hybrids were obtained by thermal property analysis (TPS) at room temperature and above melting temperatures of the salts. The highest increase in thermal conductivity was observed as 73% for KNO3/AAO-35 nm. For NaNO3/AAO-380 nm hybrids, the thermal conductivity coefficient was 1.224 ± 0.019 at room temperature. To determine the capacity and efficiency of MS/AAO hybrids during the heat transfer process, the energy storage density per unit volume (J m-3) was calculated. The highest energy storage capacity was calculated as 2390 MJ m-3 for KNO3/AAO with a pore diameter of 400 nm. This value is approximately five times higher than that of bulk salt.

Non-equilibrium Effects of Polymer Dynamics under Nanometer Confinement: Effects of Architecture and Molar Mass.

The non-equilibrium dynamics of linear and star-shaped cis-1,4 polyisoprenes confined within nanoporous alumina is explored as a function of pore size, d, molar mass, and functionality (f = 2, 6, and 64). Two thermal protocols are tested: one resembling a quasi-static process (I) and another involving fast cooling followed by annealing (II). Although both protocols give identical equilibrium times, it is through protocol I that it is easier to extract the equilibrium times, teq, by the linear relationships of the characteristic peak frequencies with time and rate, respectively, as log(fmax) = C1 - k log(t) and log(fmax) = C2 + λ log(ß). Both thermal protocols establish the existence of a critical temperature (at Tc, where k → 0 and λ → 0) below which non-equilibrium effects set-in. The critical temperature depends on the degree of confinement, 2Rg/d, and on molecular architecture. Strikingly, establishing equilibrium dynamics at all temperatures above the bulk, Tg, requires 2Rg/d ∼ 0.02, i.e., pore diameters that are much larger than the chain dimensions. This reflects non-equilibrium configurations of the adsorbed layer that extent away from the pore walls. The equilibrium times depend strongly on temperature, pore size, and functionality. In general, star-shaped polymers require longer times to reach equilibrium because of the higher tendency for adsorption. Both thermal protocols produced an increasing dielectric strength for the segmental and chain modes. The increase was beyond any densification, suggesting enhanced orientation correlations of subchain dipoles.

Bio-inspired adhesion control with liquids.

Bio-inspired surfaces enabling wet adhesion management are of significant interest for applications in the field of biomedicine, as components of bionic robots and as wearable devices. In the course of biological evolution, many organisms have evolved wet adhesive surfaces with strong attachment ability. Insects enhance their adhesion on contact substrates using secreted adhesive liquids. Here we discuss concepts of bio-inspired wet adhesion. First, remaining challenges associated with the understanding and the design of biological and artificial wet adhesive systems as well as strategies to supply adhesive liquids to their contact surfaces are reviewed. Then, future directions to construct wet adhesive surfaces with liquids are discussed in detail. Finally, a model of wet adhesion management with liquids is suggested, which might help the design of next-generation bio-inspired wet adhesive surfaces.

Effect of confinement on the dynamics of 1-propanol and other monohydroxy alcohols.

We report the effect of confinement on the dynamics of three monohydroxy alcohols (1-propanol, 2-ethyl-1-hexanol, and 4-methyl-3-heptanol) differing in their chemical structure and, consequently, in the dielectric strength of the "Debye" process. Density functional theory calculations in bulk 1-propanol identified both linear and ring-like associations composed of up to five repeat units. The simulation results revealed that the ring structures, with a low dipole moment (∼2 D), are energetically preferred over the linear assemblies with a dipole moment of 2.18 D per repeat unit. Under confinement in nanoporous alumina (in templates with pore diameters ranging from 400 to 20 nm), all dynamic processes were found to speed up irrespective of the molecular architecture. The characteristic freezing temperatures of the α and the Debye-like processes followed the pore size dependence: Ta,D=Ta,D bulk-A/d1/2, where d is the pore diameter. The characteristic "freezing" temperatures for the Debye-like (the slow process for confined 1-propanol is non-Debye) and the α-processes decrease, respectively, by 6.5 and 13 K in confined 1-propanol, by 9.5 and 19 K in confined 2-ethyl-1-hexanol, and by 9 and 23 K in confined 4-methyl-3-heptanol within the same 25 nm pores. In 2-ethyl-1-hexanol, confinement reduced the number of linearly associated repeats from approximately heptamers in the bulk to dimers within 25 pores. In addition, the slower process in bulk 2-ethyl-1-hexanol and 4-methyl-3-heptanol, where the signal is dominated by ring-like supramolecular assemblies, is clearly non-Debye. The results suggest that the effect of confinement is dominant in the latter assemblies.

Phenolic Resin Dual-Use Stamps for Capillary Stamping and Decal Transfer Printing.

We report an optimized two-step thermopolymerization process carried out in contact with micropatterned molds that yields porous phenolic resin dual-use stamps with topographically micropatterned contact surfaces. With these stamps, two different parallel additive substrate manufacturing methods can be executed: capillary stamping and decal transfer microlithography. Under moderate contact pressures, the porous phenolic resin stamps are used for nondestructive ink transfer to substrates by capillary stamping. Continuous ink supply through the pore systems to the contact surfaces of the porous phenolic resin stamps enables multiple successive stamp-substrate contacts for lithographic ink deposition under ambient conditions. No deterioration of the quality of the deposited pattern occurs, and no interruptions for ink replenishment are required. Under a high contact pressure, porous phenolic resin stamps are used for decal transfer printing. In this way, the tips of the stamps' contact elements are lithographically transferred to counterpart substrates. The granular nature of the phenolic resin facilitates the rupture of the contact elements upon stamp retraction. The deposited phenolic resin micropatterns characterized by abundance of exposed hydroxyl groups are used as generic anchoring sites for further application-specific functionalizations. As an example, we deposited phenolic resin micropatterns on quartz crystal microbalance resonators and further functionalized them with polyethylenimine for preconcentration sensing of humidity and gaseous formic acid. We envision that also preconcentration coatings for other sensing methods, such as attenuated total reflection infrared spectroscopy and surface plasmon resonance spectroscopy, are accessible by this functionalization algorithm.

Fast Evaporation Enabled Ultrathin Polymer Coatings on Nanoporous Substrates for Highly Permeable Membranes.

Thin polymer coatings covering on porous substrates are a common composite structure required in numerous applications, including membrane separation, and there is a strong need to push the coating thicknesses down to the nanometer scale to maximize the performances. However, producing such ultrathin polymer coatings in a facile and efficient way remains a big challenge. Here, uniform ultrathin polymer covering films (UPCFs) are realized by a facile and general approach based on rapid solvent evaporation. By fast evaporating dilute polymer solutions spread on the surface of porous substrates, we obtain ultrathin coatings (down to ∼30 nm) exclusively on the top surface of porous substrates, forming UPCFs with a block copolymer of polystyrene-block-poly(2-vinyl pyridine) at room temperature or a homopolymer of poly(vinyl alcohol) (PVA) at elevated temperatures. Upon selective swelling of the block copolymer and crosslinking of PVA, we obtain highly permeable membranes delivering ∼2-10 times higher permeance in ultrafiltration and pervaporation than state-of-the-art membranes with comparable selectivities. We have invented a very convenient but highly efficient process for the direct preparation of defective-free ultrathin coatings on porous substrates, which is extremely desired in different fields in addition to membrane separation.

Porous block copolymer separation membranes for 21st century sanitation and hygiene.

Removing hazardous particulate and macromolecular contaminants as well as viruses with sizes from a few nm up to the 100 nm-range from water and air is crucial for ensuring sufficient sanitation and hygiene for a growing world population. To this end, high-performance separation membranes are needed that combine high permeance, high selectivity and sufficient mechanical stability under operating conditions. However, design features of separation membranes enhancing permeance reduce selectivity and vice versa. Membrane configurations combining high permeance and high selectivity suffer in turn from a lack of mechanical robustness. These problems may be tackled by using block copolymers (BCPs) as a material platform for the design of separation membranes. BCPs are macromolecules that consist of two or more chemically distinct block segments, which undergo microphase separation yielding a wealth of ordered nanoscopic domain structures. Various methods allow the transformation of these nanoscopic domain structures into customized nanopore systems with pore sizes in the sub-100 nm range and with narrow pore size distributions. This tutorial review summarizes design strategies for nanoporous state-of-the-art BCP separation membranes, their preparation, their device integration and their use for water purification.

Sensitivity of PS/CoPd Janus particles to an external magnetic field.

The dual nature of Janus particles confers fascinating properties such as a response to multiple stimuli. In this communication, we systematically study the sensitivity to a uniform external magnetic field of isolated Janus rod-shaped and spherical particles in water confined to two dimensions. The Janus asymmetry of the particles is given by magnetic [Co(0.28 nm)/Pd(0.90 nm)]8 multilayer films deposited onto monodisperse polystyrene (PS) nanorods and microspheres, respectively. It is shown that the particles dispersed in water respond to weak magnetic field applied in in-plane direction. Here we demonstrate that a precise control of the in-plane particle orientation can be obtained for magnetic field strengths higher than 0.1 mT for microspheres and 0.4 mT for nanorods.

Cationic Ordering and Its Influence on the Magnetic Properties of Co-Rich Cobalt Ferrite Thin Films Prepared by Reactive Solid Phase Epitaxy on Nb-Doped SrTiO3(001).

Here, we present the (element-specific) magnetic properties and cation ordering for ultrathin Co-rich cobalt ferrite films. Two Co-rich CoxFe3-xO4 films with different stoichiometry (x=1.1 and x=1.4) have been formed by reactive solid phase epitaxy due to post-deposition annealing from epitaxial CoO/Fe3O4 bilayers deposited before on Nb-doped SrTiO3(001). The electronic structure, stoichiometry and homogeneity of the cation distribution of the resulting cobalt ferrite films were verified by angle-resolved hard X-ray photoelectron spectroscopy. From X-ray magnetic circular dichroism measurements, the occupancies of the different sublattices were determined using charge-transfer multiplet calculations. For both ferrite films, a partially inverse spinel structure is found with increased amount of Co3+ cations in the low-spin state on octahedral sites for the Co1.4Fe1.6O4 film. These findings concur with the results obtained by superconducting quantum interference device measurements. Further, the latter measurements revealed the presence of an additional soft magnetic phase probably due to cobalt ferrite islands emerging from the surface, as suggested by atomic force microscope measurements.

Nanometer Confinement Induces Nematic Order in 1-Dodecanol.

The phase state and molecular dynamics of 1-dodecanol are studied in the bulk and under nanometer confinement within self-ordered nanoporous alumina templates. A rotator phase in the bulk is absent under confinement. A nematic liquid crystalline phase is formed instead in pores with diameters from 400 down to 25 nm. Results are based on the changes in temperature-dependence of dielectric permittivity and X-ray diffraction. The phase diagram under confinement is explored, and the limits of the nematic-to-isotropic and crystalline-to-nematic phase transitions are identified. The phase diagram allows for a direct transition from the liquid to the low-temperature crystalline phase in pores with a diameter below 20 nm. Furthermore, we report on the dielectric fingerprint of the rotator phase and the molecular dynamics in bulk 1-dodecanol.