Controlling Microstructure-Transport Interplay in Poly(ether-block-amide) Multiblock Copolymer Gas Separation Membranes.

In this study, we investigated the effect of morphology on the gas-transport properties of a poly(ether-block-amide) (PEBA) multiblock copolymer. We annealed the copolymer samples and varied the annealing temperature to evaluate the influence of changes in the microstructure on the gas transport properties of PEBA. In addition, we used time-resolved attenuated total reflection Fourier transform infrared spectroscopy to evaluate the diffusion coefficient of CO2 in PEBA based on the Fickian model. The effect of the annealing temperature on the microphase-separated structure of the multiblock copolymer is discussed in detail. Furthermore, the gas diffusivity was significantly affected by the purity of the soft domains. The annealed sample demonstrated a 38% increase in CO2 permeability while maintaining a high CO2/N2 permselectivity of approximately 53. The findings of this study provide valuable insight into the design and optimization of PEBA membranes for gas separation applications.

Curvature Effect in Polydimethylsiloxane Interaction with CO2. Insights from Theory.

In this study we employ density functional theory to investigate the binding interaction between polydimethylsiloxane and CO2 for application in gas separation membranes. The binding strength has been studied systematically as a function of the monomer conformational rotations in the polymer chain. Our work identified major differences between the CO2 interaction with the helical conformation and the linear conformation of polydimethylsiloxane polymer chains. We have further estimated dependence between the CO2 binding strength and the polydimethylsiloxane polymer chain curvature by systematically evaluating the CO2 binding to cyclic polydimethylsiloxane oligomers. The enhanced CO2 interaction with helical chains and cyclic oligomers was attributed to cooperative, confinement effects, and local electron density distribution at the Si-O-Si fragments. The binding modes were identified using vibration frequency analysis.

Aryl/Heteroaryl Substituted Boron-Difluoride Complexes Bearing 2-(Isoquinol-1-yl)pyrrole Ligands Exhibiting High Luminescence Efficiency with a Large Stokes Shift.

A series of 2-(isoquinol-1-yl)pyrrole-boron complexes possessing (hetero)aryl substituents on the pyrrole and/or isoquinoline moiety were prepared. These compounds exhibited the fluorescence emission character in both solution and solid state. In most cases, the large Stokes shift and high fluorescence quantum yield in the solution were compatible. Furthermore, the structural diversity allowed the precise tuning of emitting colors from light blue to red with strong emission intensity. The present paper describes their comprehensive optical characteristics dependent on the type and position of the substituted aryl groups by the experimental and computational studies.

Robust, Hyper-Permeable Nanomembrane Composites of Poly(dimethylsiloxane) and Cellulose Nanofibers.

Robust, nanometer-thick, permselective membranes were developed by composite formation from poly(dimethylsiloxane) (PDMS) and cellulose nanofibers (CNF). Their unique behavior is discussed in relation to that of a single-component PDMS nanomembrane. In the absence of the CNF component, the PDMS nanomembrane with a thickness of 34 nm displays ultrahigh permeability of CO2 gas, which is only ca. one order of magnitude smaller than that of free-flowing gases through a porous poly(acrylonitrile) support film (PAN, thickness 150 µm). The constant CO2/N2 selectivity observed for the whole range of membrane thickness (34 nm-10 µm) suggests that in the single-component membrane, the kinetic process at the membrane surface determines the permselective behavior. Multilayered composite membranes are obtainable by repeated spin coating. The mechanical weakness of the single-component PDMS membrane is improved by complexation with CNF, as confirmed by the bulge test and the ease of macroscopic handling. Such a robust PDMS-CNF nanomembrane gives superior permeation of 50,000 GPU with a defect-free PDMS layer of ca. 17 nm thickness. Interestingly, the permeation characteristics of the composite membrane are strongly affected by the asymmetric arrangement of PDMS and CNF layers, and the gas permeation from the side of the CNF layer is drastically reduced. The PDMS composite membrane is expected to provide practically useful systems as a means of direct air capture.

"Artificial Wood" Lignocellulosic Membranes: Influence of Kraft Lignin on the Properties and Gas Transport in Tunicate-Based Nanocellulose Composites.

Nanocellulose membranes based on tunicate-derived cellulose nanofibers, starch, and ~5% wood-derived lignin were investigated using three different types of lignin. The addition of lignin into cellulose membranes increased the specific surface area (from 5 to ~50 m2/g), however the fine porous geometry of the nanocellulose with characteristic pores below 10 nm in diameter remained similar for all membranes. The permeation of H2, CO2, N2, and O2 through the membranes was investigated and a characteristic Knudsen diffusion through the membranes was observed at a rate proportional to the inverse of their molecular sizes. Permeability values, however, varied significantly between samples containing different lignins, ranging from several to thousands of barrers (10-10 cm3 (STP) cm cm-2 s-1 cmHg-1cm), and were related to the observed morphology and lignin distribution inside the membranes. Additionally, the addition of ~5% lignin resulted in a significant increase in tensile strength from 3 GPa to ~6-7 GPa, but did not change thermal properties (glass transition or thermal stability). Overall, the combination of plant-derived lignin as a filler or binder in cellulose-starch composites with a sea-animal derived nanocellulose presents an interesting new approach for the fabrication of membranes from abundant bio-derived materials. Future studies should focus on the optimization of these types of membranes for the selective and fast transport of gases needed for a variety of industrial separation processes.

Critical Role of the Molecular Interface in Double-Layered Pebax-1657/PDMS Nanomembranes for Highly Efficient CO2/N2 Gas Separation.

In this work, we deposited a CO2-selective block copolymer, Pebax-1657, as a selective layer with a thickness of 2-20 nm on the oxygen plasma-activated surface of poly(dimethylsiloxane) (PDMS) used as a gutter layer (thickness ∼400 nm). This double-layered structure was subsequently transferred onto the polyacrylonitrile (PAN) microporous support and studied for CO2/N2 separation. The effect of interfacial molecular arrangements between the selective and gutter layers on CO2 permeance and selectivity has been investigated. We have revealed that the gas permeance and selectivity do not follow the conventional theoretical predictions for the multilayer membrane (resistance in series transport model); specifically, more selective CO2/N2 separation membranes were achieved with ultrathin selective layers. Detailed characterization of the chemical structure of the outermost membrane surface suggests that nanoscale blending of the ultrathin Pebax-1657 layer with O2 plasma-activated PDMS chains on the surface takes place. This nanoblending at the interface between the selective and gutter layers played a critical role in enhancing the CO2/N2 selectivity. CO2 permeances in the developed thin-film composite membranes (TFCM) were between 1200 and 3500 gas permeance units (GPU) and the respective CO2/N2 selectivities were between 72 and 23, providing the gas separation performance suitable for CO2 capture in postcombustion processes. This interpenetrating polymer interface enhanced the overall selectivity of the membrane significantly, exceeding the separation ability of the pristine Pebax-1657 polymer.

Structure and Properties of Hybrid Film Fabricated by Spin-Assisted Layer-by-Layer Assembly of Sacran and Imogolite Nanotubes.

A free-standing (biomacomolecule/synthetic inorganic nanotubes) hybrid film was fabricated through an alternative layer-by-layer (LBL) assembly of sacran and imogolite nanotubes. Sacran is a natural polysaccharide extracted from the cyanobacterium Aphanothece sacrum, while imogolite is a natural tubular aluminosilicate clay found in volcano ash. The hybrid film thickness increased linearly with the number of the bilayers, because of the interaction between the negatively charged surface of sacran and the positively charged surface of imogolite. UV-vis spectroscopy indicated that the LBL film exhibited good transparency. The surface morphology of the LBL film was smooth in the micrometer scale; many imogolite nanotubes were adsorbed onto the sacran layer, while no imogolite clusters were observed. Furthermore, the structure, stability, gas permeability, and mechanical properties of the LBL films were investigated.

Fast Hydrophobicity Recovery of the Surface-Hydrophilic Poly(dimethylsiloxane) Films Caused by Rechemisorption of Dimethylsiloxane Derivatives.

Long-term stability of the surface hydrophilicity of poly(dimethylsiloxane) (PDMS) remains a critical issue for a wide range of applications including, e.g., biomedical materials, biochip devices, and microfluidics. Although several mechanisms for recovering hydrophobicity have been proposed, none has been proven unequivocally. We discovered that the hydrophobic recovery of surface-oxidized PDMS films was accelerated when the films were stored in a closed chamber under an atmosphere containing dimethylsiloxane derivatives such as octamethylcyclotetrasiloxane, which had evaporated from the films and were detected by gas chromatography-mass spectrometry measurements. X-ray photoelectron spectroscopy and quartz crystal microbalance measurements were used to monitor the chemical deposition of the derivatives on the surface-oxidized substrates, and the formation of a hydrophobic dimethyl silicone layer rendered the oxidized surfaces hydrophobic again. In the absence of superficial hydrophilic functional groups, volatile species did not react with the surface, and the hydrophobic dimethyl silicone layer did not form. The results show that the formation of a thin layer of dimethylsiloxane derivatives by chemisorption is a new mechanism for recovering the surface hydrophobicity of PDMS films.

Study of Gases Permeation in Necklace-Shaped Dimethylsiloxane Polymers Bearing POSS Cages.

The transport of small gases (H2, CO2, N2, O2) through a series of novel membranes based on necklace-shaped inorganic polymers (DMS@POSS), in which a polyhedral oligomeric silsesquioxane (POSS) cage unit and soft chains of oligo-dimethyl siloxane (DMS) were alternately connected, was investigated. The influence of the DMS chain length and crosslinking density of the DMS@POSS on membrane properties were studied. The membranes revealed characteristic structure-property relation towards both glass transition and gases transport. Specifically, clear dependence of properties from the length of DMS units (or overall siloxane content) was revealed. Gas transport properties, when compared to state-of-art polydimethylsiloxane and commercial silicone rubber, demonstrated significantly higher selectivity of DMS@POSS for carbon dioxide (in CO2/N2), hydrogen (in H2/N2) and oxygen (in O2/N2) but lowered permeability, proportional to the amount of POSS in the material. With a precise control over mechanical and thermal properties compared to conventional silicone rubbers, described materials could be considered as materials of choice in niche gas separation or other applications.

Thickness Effect on CO2/N2 Separation in Double Layer Pebax-1657®/PDMS Membranes.

The effect of thickness in multilayer thin-film composite membranes on gas permeation has received little attention to date, and the gas permeances of the organic polymer membranes are believed to increase by membrane thinning. Moreover, the performance of defect-free layers with known gas permeability can be effectively described using the classical resistance in series models to predict both permeance and selectivity of the composite membrane. In this work, we have investigated the Pebax®-MH1657/PDMS double layer membrane as a selective/gutter layer combination that has the potential to achieve sufficient CO2/N2 selectivity and permeance for efficient CO2 and N2 separation. CO2 and N2 transport through membranes with different thicknesses of two layers has been investigated both experimentally and with the utilization of resistance in series models. Model prediction for permeance/selectivity corresponded perfectly with experimental data for the thicker membranes. Surprisingly, a significant decrease from model predictions was observed when the thickness of the polydimethylsiloxane (PDMS) (gutter layer) became relatively small (below 2 µm thickness). Material properties changed at low thicknesses-surface treatments and influence of porous support are discussed as possible reasons for observed deviations.

Characterization of polymer-polymer type charge-transfer (CT) blend membranes for fuel cell application.

The data presented in this article are related to polymer-polymer type charge-transfer blend membranes for fuel cell application. The visible spectra of the charge-transfer (CT) blend membranes indicated formation of CT complex in the blend membranes, and behavior of CT complex formation by polymers was clarified by Job plot of the visible spectra. The effect of fluorine for membrane property and fuel cell performance of CT blend membranes were evaluated by 19F NMR and overvoltage analysis, respectively.

Membrane thinning for efficient CO2 capture.

Enhancing the fluxes in gas separation membranes is required for utilizing the membranes on a mass scale for CO2 capture. Membrane thinning is one of the most promising approaches to achieve high fluxes. In addition, sophisticated molecular transport across membranes can boost gas separation performance. In this review, we attempt to summarize the current state of CO2 separation membranes, especially from the viewpoint of thinning the selective layers and the membrane itself. The gas permeation behavior of membranes with ultimate thicknesses and their future directions are discussed.

Fabrication and Unique Optical Properties of Two-Dimensional Silver Nanorod Arrays with Nanometer Gaps on a Silicon Substrate from a Self-Assembled Template of Diblock Copolymer.

A periodic array of nanoholes was fabricated via the self-assembly of a polystyrene(PS)-b-poly(methyl methacrylate) (PMMA) block copolymer (BCP) on a silicon substrate and selective etching of the PMMA moieties. Silver nanorods (AgNRs) were then selectively deposited in the nanoholes by a galvanic displacement reaction where the pattern was hexagonally aligned according to the template. The diameter of AgNRs was controlled by changing the immersion time. Optical measurements of the AgNR arrays revealed that the extinction peak was split into two because of the electromagnetically induced transparency effect. In addition, the AgNR arrays showed a surface-enhanced Raman scattering response and were successfully transferred from a silicon substrate to a transparent and flexible polymer film while retaining the rod arrangement.

Macroscale Superlubricity of Multilayer Polyethylenimine/Graphene Oxide Coatings in Different Gas Environments.

Friction and wear decrease the efficiency and lifetimes of mechanical devices. Solving this problem will potentially lead to a significant reduction in global energy consumption. We show that multilayer polyethylenimine/graphene oxide thin films, prepared via a highly scalable layer-by-layer (LbL) deposition technique, can be used as solid lubricants. The tribological properties are investigated in air, under vacuum, in hydrogen, and in nitrogen gas environments. In all cases the coefficient of friction (COF) significantly decreased after application of the coating, and the wear life was enhanced by increasing the film thickness. The COF was lower in dry environments than in more humid environments, in contrast to traditional graphite and diamond-like carbon films. Superlubricity (COF < 0.01) was achieved for the thickest films in dry N2. Microstructural analysis of the wear debris revealed that carbon nanoparticles were formed exclusively in dry conditions (i.e., N2, vacuum), and it is postulated that these act as rolling asperities, decreasing the contact area and the COF. Density functional theory (DFT) simulations were performed on graphene oxide sheets under pressure, showing that strong hydrogen bonding occurs in the presence of intercalated water molecules compared with weak repulsion in the absence of water. It is suggested that this mechanism prevents the separation graphene oxide layers and subsequent formation of nanostructures in humid conditions.

Facile strain analysis of largely bending films by a surface-labelled grating method.

Mechanical properties of flexible films, for example surface strain of largely bending films, are key to design of stretchable electronic devices, wearable biointegrated devices, and soft microactuators/robots. However, existing methods are mainly based on strain-gauge measurements that require miniaturized array sensors, lead wires, and complicated calibrations. Here we introduce a facile method, based on surface-labelled gratings, for two-dimensional evaluation of surface strains in largely bending films. With this technique, we demonstrate that soft-matter mechanics can be distinct from the mechanics of hard materials. In particular, liquid-crystalline elastomers may undergo unconventional bending in three dimensions, in which both the inner and outer surfaces of the bending film are compressed. We also show that this method can be applied to amorphous elastomeric films, which highlights the general importance of this new mechanical evaluation tool in designing soft-matter-based electronic/photonic as well as biointegrated materials.

Direct electrochemistry and intramolecular electron transfer of ascorbate oxidase confined on L-cysteine self-assembled gold electrode.

A direct electrochemistry and intramolecular electron transfer of multicopper oxidases are of a great importance for the fabrication of these enzyme-based bioelectrochemical-devices. Ascorbate oxidase from Acremonium sp. (ASOM) has been successfully immobilized via a chemisorptive interaction on the l-cysteine self-assembled monolayer modified gold electrode (cys-SAM/AuE). Thermodynamics and kinetics of adsorption of ASOM on the cys-SAM/AuE were studied using cyclic voltammetry. A well-defined redox wave centered at 166±3mV (vs. Ag│AgCl│KCl(sat.)) was observed in 5.0mM phosphate buffer solution (pH7.0) at the fabricated ASOM electrode, abbreviated as ASOM/cys-SAM/AuE, confirming a direct electrochemistry, i.e., a direct electron transfer (DET) between ASOM and cys-SAM/AuE. The direct electrochemistry of ASOM was further confirmed by taking into account the chemical oxidation of ascorbic acid (AA) by O2 via an intramolecular electron transfer in the ASOM as well as the electrocatalytic oxidation of AA at the ASOM/cys-SAM/AuE. Thermodynamics and kinetics of the adsorption of ASOM on the cys-SAM/AuE have been elaborated along with its direct electron transfer at the modified electrodes on the basis of its intramolecular electron transfer and electrocatalytic activity towards ascorbic acid oxidation and O2 reduction. ASOM saturated surface area was obtained as 2.41×10(-11)molcm(-2) with the apparent adsorption coefficient of 1.63×10(6)Lmol(-1). The ASOM confined on the cys-SAM/AuE possesses its essential enzymatic function.

A palladium-nanoparticle and silicon-nanowire-array hybrid: a platform for catalytic heterogeneous reactions.

We report the development of a silicon nanowire array-stabilized palladium nanoparticle catalyst, SiNA-Pd. Its use in the palladium-catalyzed Mizoroki-Heck reaction, the hydrogenation of an alkene, the hydrogenolysis of nitrobenzene, the hydrosilylation of an α,ß-unsaturated ketone, and the C-H bond functionalization reactions of thiophenes and indoles achieved a quantitative production with high reusability. The catalytic activity reached several hundred-mol ppb of palladium, reaching a TON of 2 000 000.

o-Phenylene octamers as surface modifiers for homeotropic columnar ordering of discotic liquid crystals.

Large-area homeotropic columnar ordering of π-conjugated discotic liquid crystals (LCs) is crucial for certain device applications but generally hard to achieve. Here we report polymeric o-phenylene octamer poly-1 and its monomer 1 as the first surface modifiers for homeotropic columnar order of a variety of discotic LCs up to a macroscopic length scale. Their octameric o-phenylene parts are known to fold helically into a cylinder that is reminiscent of a π-stacked column of discotic LCs. Through-view X-ray diffraction patterns of 1 suggested that this molecule adheres to the glass substrate and directs its cylindrical axis perpendicular to the glass surface. This "face-on" orientation likely nucleates the homeotropic columnar order of discotic LC materials.

Molecular Insight into Different Denaturing Efficiency of Urea, Guanidinium, and Methanol: A Comparative Simulation Study.

We have designed various nanoslit systems, whose opposing surfaces can be either hydrophobic, hydrophilic, or simply a water-vapor interface, for the molecular dynamics simulation of confined water with three different protein denaturants, i.e., urea, guanidinium chloride (GdmCl), and methanol, respectively. Particular attention is placed on the preferential adsorption of the denaturant molecules onto the opposing surfaces and associated resident time in the vicinal layer next to the surfaces, as well as their implication in the denaturing efficiency of different denaturant molecules. Our simulation results show that among the three denaturants, the occupancy of methanol in the vicinal layer is the highest while the residence time of Gdm is the longest. Although the occupancy and the residence time of urea in the vicinal layer is less than those of the other two denaturant molecules, urea entails "all-around" properties for being a highly effective denaturant. The distinct characteristics of three denaturants may suggest a different molecular mechanism for the protein denaturation. This comparative simulation by design allows us to gain additional insights, on the molecular level, into the denaturation effect and related hydrophobic effect.

Sensitivity to refractive index of high-aspect-ratio nanofins with optical vortex.

An easy and large-scale fabrication technique of metal fins was used to produce periodic Au fin arrays that realized light confinement in the near-infrared region. Light confinement was revealed by vortex patterns in the optical power flow of an array of high-aspect-ratio fins (height of 1000 nm for a width of 50 nm). The light confinement resulted in sharp dips in the reflectance spectrum of the high-aspect-ratio fin array. The wavelengths of the reflectance dips were found to shift toward higher values when the refractive index of the surrounding medium was increased. Experimental and simulated dip shift values were in good agreement with a demonstrated sensitivity of 580 nm per refractive index unit.