pH-Responsive Ultrathin Nanoporous SiO2 Films for Selective Ion Permeation.

Ultrathin nanoporous (NP) films are an emerging field for selective and effective ion/molecular separation and electrochemical sensing applications. We describe selective ion permeation in surface-functionalized ultrathin NP SiO2 films (NP SiO2-NH2). The ultrathin NP SiO2 films with ca. 8 nm thickness were prepared from silsesquioxane-containing blend polymer Langmuir-Blodgett films (nanosheets) using the photo-oxidation method. The porous SiO2 surface was modified with a pH-responsive amine-containing silane coupling agent. Selective ion permeation was demonstrated under acidic pH conditions (pH ≤ 6) using two equally sized redox probes: negative (Fe(CN)63-/4-) and positive (Ru(NH3)62+/3+) ions. The current density for Fe(CN)63-/4- decreased as the pH value increased to pH = 6, whereas it increased for Ru(NH3)62+/3+. Control measurements revealed that the probes can penetrate the pores of nonfunctionalized SiO2 films irrespective of pH values, indicating that both the size and the surface charge response contributed to selective ion permeation. Results obtained from this study pave the way for new applications in molecular separation and sensing applications based on ultrathin nanoporous films (<10 nm) and tailored surfaces.

Titania Nanofilms from Titanium Complex-Containing Polymer Langmuir-Blodgett Films.

This paper proposes a method of fabricating low-dimensional TiO2 nanofilms at room temperature under ambient pressure conditions. The titanium-containing polymer complex Ti-p(DDA/acac) was synthesized by reacting an amphiphilic copolymer (p(DDA/acac)) with a titanium complex. Its ultrathin films were prepared using the Langmuir-Blodgett (LB) technique. The monolayer was found to be free from hydrolysis and cross-linking side reactions, even at the air-water interface. The transferred LB films (nanosheets) were oxidized by ultraviolet irradiation at room temperature. The photo-oxidized material has an amorphous and porous structure with subnanometer-scale controllability (0.18 nm per layer). Photocatalytic performance was demonstrated by converting multilayered LB films of Ti-(DDA/acac) and the silicon-containing polymer p(DDA/SQ) into ultrathin hetero-multilayers of TiO2 and SiO2 under UV-O3 treatment. The scalability affords a uniform photopattern formation of photo-oxidized TiO2 films over several hundreds of micrometers.

Synthesis of metallo-supramolecular materials based on terpyridine functionalized double-decker silsesquioxane with improved complexation efficiency.

Silsesquioxane-based transition-metal complexes have come to the forefront due to the ability of silsesquioxane to control nanostructures and properties. However, some difficulties in complete complexation and purification limit the widespread use of transition-metal-based supramolecular coordination complexes comprising silsesquioxane. Herein, 2 different approaches have been proposed for the synthesis of metallo-supramolecular materials on the basis of ruthenium(II)-terpyridine functional double-layer silsesquioxane (DDSQ) (Tpy/Ru-DDSQ) (Routes 1 and 2). In Route 1, complexation was followed by functionalization of DDSQ with the ligand, whereas in Route 2, complexation was performed before the ligand was inserted into the DDSQ. Tpy/Ru-DDSQ obtained from both approaches was characterized by 1H NMR, X-ray photoelectron spectrometer, and FTIR and found in the same structure. Both methods were fully discussed and their merits were explored. The complexation yield of the routes was similar. However, the results based on NMR and UV-Vis spectroscopy demonstrated that the incorporation rate of DDSQ into the complex was quite high in Route 2. As far as is known, this is the first study based on the effects of complexing Tpy ligands before/after binding to the target compound, particularly to silsesquioxane-based materials.

Cellulose Nanofiber Nanosheet Multilayers by the Langmuir-Blodgett Technique.

We describe a systematic approach for producing cellulose nanofiber (CNF) nanosheets using the Langmuir-Blodgett (LB) technique. The CNFs were obtained from sulfuric acid hydrolysis of commercially available microfibrillated cellulose. Needle-like CNFs, negatively charged by grafted sulfate groups, were maintained at the air-water interface, assisted by amphiphilic polymer, poly( N-dodecyl acrylamide) (pDDA). The CNFs produced a stable monolayer. The surface pressure increased steadily with a high collapse pressure of 50 mN m-1 when spread with formic acid and pDDA. The composite monolayers were transferred onto solid substrates as Y-type LB films using a vertical dipping method. Upstroke and downstroke transfer ratios of the films were, respectively, unity and 0.88, indicating that full coverage was achieved by the monolayer even for more than 200 layers. Results obtained using atomic force microscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy showed that CNF nanosheets possess well-defined layer structures with average monolayer thickness of 5.3 nm. The relative amount of CNFs in the nanosheets was calculated as 62.6 wt % using the quartz crystal microbalance technique. The as-prepared nanosheets are optically transparent to visible light and have high hydrophobicity. In fact, the nanosheet transparency was higher than 88% at 600 nm wavelength for 24 layers. A miniscule amount of pDDA enables demonstration of free-standing CNF nanosheets with 1 cm width and 45.6 nm thickness (23 layers).

Biomimetic Polyelectrolytes Based on Polymer Nanosheet Films and Their Proton Conduction Mechanism.

We report a biomimetic polyelectrolyte based on amphiphilic polymer nanosheet multilayer films. Copolymers of poly( N-dodecylacrylamide- co-vinylphosphonic acid) [p(DDA/VPA)] form a uniform monolayer at the air-water interface. By depositing such monolayers onto solid substrates using the Langmuir-Blodgett (LB) method, multilayer lamellae films with a structure similar to a bilayer membrane were fabricated. The proton conductivity at the hydrophilic interlayer of the lamellar multilayer films was studied by impedance spectroscopy under temperature- and humidity-controlled conditions. At 60 °C and 98% relative humidity (RH), the conductivity increased with increasing mole fraction of VPA ( n) up to 3.2 × 10-2 S cm-1 for n = 0.41. For a film with n = 0.45, the conductivity decreased to 2.2 × 10-2 S cm-1 despite the increase of proton sources. The reason for this decrease was evaluated by studying the effect of the distance between the VPAs ( lVPA) on the proton conductivity as well as their activation energy. We propose that for n = 0.41, lVPA is the optimal distance not only to form an efficient two-dimensional (2D) hydrogen bonding network but also to reorient water and VPA. For n = 0.45, on the other hand, the lVPA was too close for a reorientation. Therefore, we concluded that there should be an optimal distance to obtain high proton conductivity at the hydrophilic interlayer of such multilayer films.

High-Density and Monolayer-Level Integration of π-Conjugated Units: Amphiphilic Carbazole Homopolymer Langmuir-Blodgett Films.

Precise integration of π-conjugated units is a key issue to achieve molecular (nano) electronic devices based on organic semiconductor materials. We specifically examine the Langmuir-Blodgett technique, which allows high-density integration of π-conjugated units. In this study, we designed a carbazole containing acrylamide-based homopolymer [poly(9-ethyl-3-carbazolyl acrylamide) (pCzAA)], in which the π-conjugated unit is connected with a hydrophilic amide unit directly as a side chain. Its Langmuir-Blodgett film formation properties were investigated. The pCzAA polymer took a stable monolayer formation in the presence of a small amount (ca. 10 mol %) of poly( N-dodecylacrylamide) (pDDA). Compared with amphiphilic carbazole-containing copolymers described in earlier reports, the direct connection of π-conjugated units through amide bonding enables the Cz content in monolayers to exceed that of the copolymer monolayers (ca. 30 mol %) dramatically. pCzAA:pDDA takes highly ordered layer structures toward the out-of-plane direction, although no structural order is formed in the in-plane direction. This method is a practical means to develop low-dimensional and high-density integration of π-conjugated units for molecular electronics.

Synthesis and Porous SiO2 Nanofilm Formation of the Silsesquioxane-Containing Amphiphilic Block Copolymer.

We describe the synthesis, Langmuir-Blodgett (LB) film formation, and photo-oxidation of an organic-inorganic hybrid block copolymer consisting of N-dodecyl acrylamide (DDA) and silsesquioxane (SQ) comonomers [p(DDA/SQ26)- b-pDDA]. The copolymer was synthesized by reversible addition fragmentation chain transfer polymerization of DDA and SQ. Higher monolayer stability at the air-water interface was confirmed for p(DDA/SQ26)- b-pDDA. The p(DDA/SQ26)- b-pDDA monolayer was deposited onto solid substrates with a monolayer thickness of 2.3 nm. The photo-oxidized SiO2 nanofilm revealed its porous structure, which reflects phase-separated structures of p(DDA/SQ26)- b-pDDA, as confirmed using atomic force microscopy, quartz crystal microbalance, and cyclic voltammetry measurements. These results demonstrate that this preparation method using photo-oxidation of the organic-inorganic hybrid block copolymer LB film is promising for manipulating pore formations of inorganic oxide nanofilms.

Resistive switching of organic-inorganic hybrid devices of conductive polymer and permeable ultra-thin SiO2 films.

We propose a resistive switching device composed of conductive polymer (PEDOT:PSS) and SiO2 ultra-thin films. The SiO2 film was fabricated from silsesquioxane polymer nanosheets as a resistive switching layer. Devices with metal (Ag or Au)∣SiO2∣PEDOT:PSS architecture show good resistive switching performance with set-reset voltages as low as several hundred millivolts. The device properties and the working mechanism were investigated by varying the electrode material, surrounding atmosphere, and SiO2 film thickness. Results show that resistive switching is based on water and ion migration at the PEDOT:PSS∣SiO2 interface.

Resistive non-volatile memories fabricated with poly(vinylidene fluoride)/poly(thiophene) blend nanosheets.

Ferroelectric poly(vinylidene fluoride)/semiconductive polythiophene (P3CPenT) blend monolayers were developed at varying blend ratios using the Langmuir-Blodgett technique. The multilayered blend nanosheets show much improved surface roughness that is more applicable for electronics applications than spin-cast films. Because of the precisely controllable bottom-up construction, semiconductive P3CPenT were well dispersed into the ferroelectric PVDF matrix. Moreover, the ferroelectric matrix contains almost 100% ß crystals: a polar crystal phase responsible for the ferroelectricity of PVDF. Both the good dispersion of semiconductive P3CPenT and the outstanding ferroelectricity of the PVDF matrix in the blend nanosheets guaranteed the success of ferroelectric organic non-volatile memories based on ferroelectricity-manipulated resistive switching with a fresh high ON/OFF ratio and long endurance to 30 days.

Synthesis and photochemical response of Ru(ii)-coordinated double-decker silsesquioxane.

A double-decker silsesquioxane based bis(terpyridine) ruthenium(ii) complex (2Tpy/Ru-DDSQ), a member of the polyhedral oligomeric silsesquioxane (POSS) class, has been synthesized. Its structure has been characterized using comprehensive techniques such as nuclear magnetic resonance (1H NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. This work not only deals with the synthesis of 2Tpy/Ru-DDSQ but also provides the first comprehensive investigation based on the photoluminescence and electrochemical features of a POSS member. With this structure, an efficient anodic photocurrent response has been obtained. This result has been attributed to the perfect arrangement of ruthenium(ii)-bis(terpyridine) (tpy) ([Ru(Tpy)2]2+) moieties in the DDSQ nano building blocks. Therefore, 2Tpy/Ru-DDSQ can be considered as a promising candidate for the development of new generation photosensitizers.

Acid-Group-Content-Dependent Proton Conductivity Mechanisms at the Interlayer of Poly(N-dodecylacrylamide-co-acrylic acid) Copolymer Multilayer Nanosheet Films.

The effect of the content of acid groups on the proton conductivity at the interlayer of polymer-nanosheet assemblies was investigated. For that purpose, amphiphilic poly(N-dodecylacrylamide-co-acrylic acid) copolymers [p(DDA/AA)] with varying contents of AA were synthesized by free radical polymerization. Surface pressure (π)-area (A) isotherms of these copolymers indicated that stable polymer monolayers are formed at the air/water interface for AA mole fraction (n) ≤ 0.49. In all cases, a uniform dispersion of the AA groups in the polymer monolayer was observed. Subsequently, polymer monolayers were transferred onto solid substrates using the Langmuir-Blodgett (LB) technique. X-ray diffraction (XRD) analyses of the multilayer films showed strong Bragg diffraction peaks, suggesting a highly uniform lamellar structure for the multilayer films. The proton conductivity of the multilayer films parallel to the direction of the layer planes were measured by impedance spectroscopy, which revealed that the conductivity increased with increasing values of n. Activation energies for proton conduction of ∼0.3 and 0.42 eV were observed for n ≥ 0.32 and n = 0.07, respectively. Interestingly, the proton conductivity of a multilayer film with n = 0.19 did not follow the Arrhenius equation. These results were interpreted in terms of the average distance between the AA groups (lAA), and it was concluded that, for n ≥ 0.32, an advanced 2D hydrogen bonding network was formed, while for n = 0.07, lAA is too long to form such hydrogen bonding networks. The lAA for n = 0.19 is intermediate to these extremes, resulting in the formation of hydrogen bonding networks at low temperatures, and disruption of these networks at high temperatures due to thermally induced motion. These results indicate that a high proton conductivity with low activation energy can be achieved, even under weakly acidic conditions, by arranging the acid groups at an optimal distance.

Regioselective Synthesis of Eight-Armed Cyclosiloxane Amphiphile for Functional 2D and 3D Assembly Motifs.

A crystalline tetramethylcyclotetrasiloxane (TMCS)-derived amphiphile was regioselectively synthesized with eight peripheral hydrophilic amide groups and hydrophobic dodecyl chains by Pt(0)-catalyzed hydrosilylation and amidation reactions. The as-synthesized materials showed ordered lamellar structure formation in the powder form. It also exhibits superior two-dimensional (2D) monolayer formation properties at the air-water interface with unexpectedly high collapse surface pressure and elastic modulus. The monolayers act as two-dimensional building blocks with finely controllable thickness on a several nanometer scale irrespective of the substrate type and properties. The amphiphile forms nanofibers spontaneously by good-poor solvent strategies, which contributes to porous three-dimensional (3D) structures possessing superhydrophobic surface wettability.

Multimodal underwater adsorption of oxide nanoparticles on catechol-based polymer nanosheets.

Multimodal underwater adsorption behaviour of catechol units was demonstrated by examining the adsorption of different oxide nanoparticles on nanoscale-integrated polymer nanosheets. Catechol-based polymer nanosheets were fabricated using the Langmuir-Blodgett (LB) technique with random copolymers (p(DDA/DMA)s) of N-dodecylacrylamide (DDA) and dopamine methacrylamide (DMA). The p(DDA/DMA) nanosheets were immersed into water dispersions of SiO2, Al2O3, and WO3 nanoparticles (NPs) respectively. The results show that the adsorption properties can be altered by varying the NP type: SiO2 NP adsorption was observed only below pH = 6, at which the o-quinone form in p(DDA/DMA) nanosheets transforms into the catechol form or vice versa. However, their transition point for Al2O3 NP adsorption was found at approximately pH 10, at which the surface potential of Al2O3 NPs changes the charge polarity, indicating that the electrostatic interaction is predominant. For WO3 NPs, adsorption was observed when citric acid, which modifies the surface of WO3 NPs by complex formation, was used as a pH-controlling agent, but no adsorption was found for hydrochloric acid used as a pH controlling agent. FT-IR measurements proved that miniscule amounts of water molecules were trapped in p(DDA/DMA) nanosheets and that they acquired hydrogen bonding network formations, which might assist nanoparticle adsorption underwater and make the catechol units adjustable. The results indicate that the nanoscale spatial arrangements of catechol units in films are crucially important for the application of multimodal adsorption of oxide nanoparticles on catechol-based polymer materials.

High proton conductivity in the molecular interlayer of a polymer nanosheet multilayer film.

High proton conductivity was achieved in a polymer multilayer film with a well-defined two-dimensional lamella structure. The multilayer film was prepared by deposition of poly(N-dodecylacryamide-co-acrylic acid) (p(DDA/AA)) monolayers onto a solid substrate using the Langmuir-Blodgett technique. Grazing-angle incidence X-ray diffraction measurement of a 30-layer film of p(DDA/AA) showed strong diffraction peaks in the out-of-plane direction at 2θ = 2.26° and 4.50°, revealing that the multilayer film had a highly uniform layered structure with a monolayer thickness of 2.0 nm. The proton conductivity of the p(DDA/AA) multilayer film parallel to the layer plane direction was 0.051 S/cm at 60 °C and 98% relative humidity with a low activation energy of 0.35 eV, which is comparable to perfluorosulfonic acid membranes. The high conductivity and low activation energy resulted from the formation of uniform two-dimensional proton-conductive nanochannels in the hydrophilic regions of the multilayer film. The proton conductivity of the multilayer film perpendicular to the layer plane was determined to be 2.1 × 10(-13) S/cm. Therefore, the multilayer film showed large anisotropic conductivity with an anisotropic ratio of 2.4 × 10(11).

Superhydrophobic porous surfaces: dissolved oxygen sensing.

Porous polymer films are necessary for dissolved gas sensor applications that combine high sensitivity with selectivity. This report describes a greatly enhanced dissolved oxygen sensor system consisting of amphiphilic acrylamide-based polymers: poly(N-(1H, 1H-pentadecafluorooctyl)-methacrylamide) (pC7F15MAA) and poly(N-dodecylacrylamide-co-5- [4-(2-methacryloyloxyethoxy-carbonyl)phenyl]-10,15,20-triphenylporphinato platinum(II)) (p(DDA/PtTPP)). The nanoparticle formation capability ensures both superhydrophobicity with a water contact angle greater than 160° and gas permeability so that molecular oxygen enters the film from water. The film was prepared by casting a mixed solution of pC7F15MAA and p(DDA/PtTPP) with AK-225 and acetic acid onto a solid substrate. The film has a porous structure comprising nanoparticle assemblies with diameters of several hundred nanometers. The film shows exceptional performance as the oxygen sensitivity reaches 126: the intensity ratio at two oxygen concentrations (I0/I40) respectively corresponding to dissolved oxygen concentration 0 and 40 (mg L(-1)). Understanding and controlling porous nanostructures are expected to provide opportunities for making selective penetration/separation of molecules occurring at the superhydrophobic surface.

Solvent-dependent properties of poly(vinylidene fluoride) monolayers at the air-water interface.

The present work addresses the solvent-dependent properties of Langmuir films of poly(vinylidene fluoride) (PVDF) and amphiphilic poly(N-dodecylacrylamide) (pDDA) at different mixing ratios. After introducing pDDA nanosheets, PVDF Langmuir films obtain a tremendously enhanced modulus as well as high transfer ratios using the vertical dipping method caused by the support of the pDDA two-dimensional hydrogen bonding network. Brewster angle microscopy (BAM) was used to investigate PVDF monolayers at the air-water interface in situ. Spreading from different solvents, the PVDF molecules take completely different aggregation states at the air-water interface. The PVDF molecules aggregate to become large domains when spread from N-methyl-2-pyrrolidone (NMP). However, the volatile and low-polarity methylethyl ketone (MEK) made the PVDF molecules more dispersive on the water surface. This study also discovers a versatile crystallization control of PVDF homopolymer from complete ß phase (NMP) to complete α phase (MEK) at the air-water interface, thereby eliciting useful information for further manipulation of film morphologies and film applications.

Flexible design of free-standing hybrid polymer nanosheets through bottom-up approach.

We describe the bottom-up design of highly ordered free-standing nanofilms consisting of polymer Langmuir-Blodgett films (polymer nanosheets). Polymer nanosheets enable the incorporation of a wide variety of functional groups such as reactive components and chromophores, which serve as building blocks of free-standing nanofilms. We demonstrated a free-standing fluorescent hybrid nanofilm in which the separation between gold nanoparticles and fluorophores was tuned at the nanometer scale. Moreover, we prepared a free-standing nanofilm consisting of a two-dimensional homogeneous nickel zinc iron oxide (NiZnFe22O4) nanoparticle monolayer assembled on polymer nanosheets.

A trilayer film approach to multicolor electrochromism.

Development of multicolored electrochromic materials is important to realize their applications in electronic devices such as full color electronic paper. One method to increase the number of colors in an electrochromic device is by color mixing. A simple method for color mixing involves two electrochromes deposited at different working electrodes. Selective control of the redox state of each electrochrome allows the generation of both the individual electrochrome colors and a mixture of the two colors. In this paper we report a new strategy that enables color mixing using a single working electrode. A trilayer film composed of an ultrathin layer of a ruthenium complex sandwiched between two layers of Prussian blue (PB) nanoparticles was prepared on an ITO electrode using the Langmuir-Blodgett technique. Cyclic voltammetry and spectroelectrochemistry of the films indicate that the redox state of PB located at the top and bottom layer can be independently controlled using a single working electrode. In this way a mixture of the colors of PB and Prussian yellow could be produced without the necessity for multiple electrodes.

Enhancement of proton transport in an oriented polypeptide thin film.

Proton transport properties of a partially protonated poly(aspartic acid)/sodium polyaspartate (P-Asp) were investigated. A remarkable enhancement of proton conductivity has been achieved in the thin film. Proton conductivity of 60-nm-thick thin film prepared on MgO(100) substrate was 3.4 × 10(-3) S cm(-1) at 298 K. The electrical conductivity of the oriented thin film was 1 order of magnitude higher than the bulk specimen, and the activation energies for the proton conductivity were 0.34 eV for the oriented thin film and 0.65 eV for the pelletized sample, respectively. This enhancement of the proton transport is attributable to the highly oriented structure on MgO(100) substrate. This result proposes great potential for a new strategy to produce a highly proton-conductive material using the concept of an oriented thin film structure without strong acid groups.