Order-order transitions in poly(N-octadecyl acrylamide-co-hydroxyethyl acrylamide) statistical copolymer films.

This study demonstrates that a simple statistical copolymer can form self-assembled lamellae, whose structures depend on both the comonomer composition and the annealing temperature. Statistical copolymers of octadecyl acrylamide and hydroxyethyl acrylamide [p(ODA/HEAm)] were prepared via free-radical copolymerization, and their thermal properties were studied by differential scanning calorimetry. Thin films of p(ODA/HEAm) were prepared via spin-coating, and their structures were analyzed using X-ray diffraction. It was found that copolymers with HEAm contents between 28 and 50% formed self-assembled lamellae upon annealing at a temperature ∼10 °C above the glass-transition temperature. The self-assembled form was found to possess a "side-chain-mixed" lamellar structure, in which the ODA and HEAm side chains are oriented perpendicular to the lamellar plane composed of the polymer main chain. Interestingly, a copolymer with a HEAm content between 36 and 50% transformed from the side-chain-mixed lamellar structure to generate a "side-chain-segregated" lamellar structure upon annealing at a significantly higher temperature (∼50 °C above Tg). In this structure, the ODA and HEAm side chains were found to be oriented in opposite directions but perpendicular to the lamellar plane. The packing of the side chains in the lamellar structures was studied using Fourier-transform infrared spectroscopy. It was concluded that the structures of the self-assembled lamellae are determined by the strain forces generated during self-assembly, and by the segregation forces existing between the comonomers.

A solvent-compatible filter-transfer method of semi-transparent carbon-nanotube electrodes stacked with silver nanowires.

Low-density films of single-walled carbon nanotubes (SWNTs) can be used as a semi-transparent top electrode for all-solution-processed film devices; however, their semiconductor characteristics vary depending on the experimental factors in their dispersion into solvents, and the sublayers are damaged as a result of solvent incompatibility. In this study, we report a solvent-compatible filter-transfer method for SWNT films stacked with silver nanowires (AgNWs), and evaluate the semiconductor characteristics through the p/n heterojunction with a Si wafer (SWNT/Si). AgNWs and SWNTs were successively filtered through their aqueous dispersion solutions using a membrane filter. The stacked semi-transparent films (AgNW/SWNT films with controlled densities) were successfully transferred onto glass plates and Si wafers. The transmittance at 550 nm revealed a window between 60% and 80% with a narrow sheet resistance range between 11 and 23 Ω â–¡-1. The power conversion efficiency (PCE) of SWNT/Si was improved to 11.2% in a junction area of 0.031 cm2 through the use of spin-coated Nafion resins; however, the accumulated resistance of SWNTs drastically reduced the PCE to 2% as the area increased to ≥0.5 cm2. AgNWs maintained the PCE within a range of 10.7% to 8.6% for an area ranging from 0.031 cm2 to 1.13 cm2. All of the photovoltaic parameters were dependent on the junction areas, suggesting that AgNWs function as an effective current-collector layer on the semiconductor layer of SWNTs without direct contact of AgNWs with the Si surface. In addition, we report a solvent-compatible experiment for transferring AgNW/SWNT films onto a solvent-sensitive perovskite material (CH3NH3PbI3).

Selective enlargement of left lateral segment liver volume as a potential diagnostic predictor for biliary atresia.

PURPOSE: To determine an early diagnostic indicator of biliary atresia (BA), we focused on morphological left-right differences of BA livers. METHODS: Of 74 infants with suspected BA at our hospital in the last 12 years, 25 met the conditions for investigation: 15 infants with BA (BA group) and 10 with other pathologies (non-BA group). CT volumetry of the liver in each patient was performed using a 3D image analysis system. Patient characteristics, blood data, and proportion of the left lateral segment to the total liver volume (LLS ratio) were compared between the two groups. RESULTS: Among the patient characteristics and liver function tests, only γ-glutamyl transpeptidase (GGT) were significantly higher in the BA group (p < 0.001). The LLS ratio was 0.321 (0.227-0.382) in the BA group and 0.243 (0.193-0.289) in the non-BA group (p = 0.01). The summary cut-off, area under the curve, sensitivity, and specificity were 0.322, 0.813, 53.3, and 100% for the LLS ratio and 94.26, 0.95, 86.7, and 100% for the GGT × LLS ratio, respectively. CONCLUSIONS: The LLS ratio is highly specific and may be an early diagnostic predictor of BA. Moreover, this segmental LLS enlargement may be associated with the etiology of BA.

Fully automated chemiluminescence enzyme immunoassays showing high correlation with immunoprecipitation mass spectrometry assays for ß-amyloid (1-40) and (1-42) in plasma samples.

Blood based ß-amyloid (Aß) assays that can predict amyloid positivity in the brain are in high demand. Current studies that utilize immunoprecipitation mass spectrometry assay (IP-MS), which has high specificity for measuring analytes, have revealed that precise plasma Aß assays have the potential to detect amyloid positivity in the brain. In this study, we developed plasma Aß40 and Aß42 immunoassays using a fully automated immunoassay platform that is used in routine clinical practice. Our assays showed high sensitivity (limit of quantification: 2.46 pg/mL [Aß40] and 0.16 pg/mL [Aß42]) and high reproducibility within-run (coefficients of variation [CVs]: <3.7% [Aß40] and <2.0% [Aß42]) and within-laboratory (CVs: <4.6% [Aß40] and <5.3% [Aß42]). The interference from plasma components was less than 10%, and the cross-reactivity with various lengths of Aß peptides was less than 0.5%. In addition, we found a significant correlation between the IP-MS method and our immunoassay (correlation coefficients of Pearson's r: 0.91 [Aß40] and 0.82 [Aß42]). Our new method to quantify plasma Aß40 and Aß42 provides clinicians and patients with a way to continuously monitor disease progression.

Self-Assembled Lamellar Films of Comb-Shaped Copolymers by Segregation between Hydrophobic Side Chains and the Main Chain with Hydrophilic Comonomers.

Self-assembled lamellar films of poly(N-dodecyl acrylamide-stat-vinyl phosphonic acid) [p(DDA/VPA)] were formed via the segregation between the hydrophilic main chain and VPA and dodecyl side chains. p(DDA/VPA) copolymers were synthesized by free-radical copolymerization of DDA and VPA with VPA molar concentrations of 19% [p(DDA/VPA19)] and 64% [p(DDA/VPA64)]. Both copolymers exhibited a glass-transition temperature (Tg) and melting temperature for p(DDA/VPA19), but no crystalline or liquid-crystalline phase-transition temperatures, which suggests that both copolymers are amorphous. Thin films of the copolymers were prepared by spin coating, and the structure of the films was studied by X-ray diffraction (XRD) measurements. The as-cast films of the copolymers showed broad diffraction patterns, which suggested the formation of alkyl nanodomains similar to that observed in the pDDA homopolymers. On the other hand, the XRD patterns for both copolymer films showed a sharp Bragg diffraction in the low-q region after annealing at 60 °C. Furthermore, the p(DDA/VPA19) film showed first- and second-order Bragg diffractions with a ratio of 1:2. These XRD patterns suggest that the copolymer films form an ordered lamellar structure. We concluded that the main chain became more hydrophilic by the introduction of VPA, resulting in an increased segregation force relative to the hydrophobic dodecyl side chains, which induces the formation of lamellae. Moreover, doping a p(DDA/VPA64) film with imidazole increased the ordering and uniformity of the lamellar structures due to the increased segregation force by the formation of ion pairs in the hydrophilic comonomer. In their entirety, the results show that statistical copolymerization can be used as a new method to create self-assembled structures.

Site-Selective Wettability Control of Honeycomb Films by UV-O3-Assisted Sol-Gel Coating.

Wettability control of porous materials is significant in lateral flow immunoassay, microfluidic systems, microdroplet manipulation, and so on. In this report, formation of metal oxide layers on self-organized polymer honeycomb films to control surface wettability by simple sol-gel coating and UV-O3 treatment was demonstrated. By the combination of bottom-up and top-down processes, silica thin layers can be formed by retaining their original three-dimensional honeycomb structures. Furthermore, photopatterning of metal oxides on honeycomb films can be achieved by UV irradiation through photomasks. Site-selective wettability control of honeycomb films was realized by patterning silica layers on the surface of the film.

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.

Interplay between two radical species in the formation of periodic patterns during a polymerization reaction.

Periodic patterns are ubiquitous in nature and spontaneously form on molecular to cosmic scales by the interplay between reaction and diffusion. Understanding how these patterns form is important to understand the construction rules of nature and apply them in the synthesis of functional artificial materials. This work clarifies how radical (R˙) species affect pattern formation in periodic precipitated and depleted zones during a polymerization process in an agarose gel. When a monomer (Mon) solution was poured on top of the gel doped with an initiator (In) in a test tube, periodic and continuous precipitation occurred near and far away from the solution/gel interface, respectively. In contrast, a system without In exhibited only a continuous band of precipitates beyond a depleted zone without precipitates at a certain distance from the interface. In the depleted region, an inhibitor (Q) added to the solution limited the polymerization triggered by R˙ formed thermally from Mon. With the addition of enough In to overcome the quenching effect of Q, periodic bands appeared near the solution/gel interface. These results suggest the involvement of two independent polymerization processes: (i) polymerization triggered by R˙ formed from In, which is the dominant process up to 100 h and yields periodic structures near the interface. After 100 h, the dominant process is the polymerization triggered by R˙ generated thermally from Mon, which yields a continuous precipitation zone. These two R˙ species compete and generate periodic bands near the interface (<100 h) and a continuous band far away from the interface (>100 h).

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.

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).

Photoconductive Properties of Dibenzotetrathiafulvalene-Tetracyanoquinodimethane (DBTTF-TCNQ) Nanorods Prepared by the Reprecipitation Method.

Charge-transfer complex crystals have been extensively studied because of their metallic conductivity, photoconductivity, ambipolar charge transport, and high career mobility. Numerous studies of their applications for organic electric devices such as organic field effect transistors and solar cells have reported. However, bulky single crystals of charge-transfer complexes are difficult to handle, specifically to be made into a form of a thin film. Recently, nano/micro crystallization of charge-transfer crystal is attracted to realize thin film applications. In this paper, charge transfer complex nanorods composed of dibenzotetrathiafulvalene-tetracyanoquinodimethane (DBTTF-TCNQ) were prepared by the reprecipitation method. The as-formed nanorods possess a kinetically metastable crystal structure different from the thermodynamically stable bulk crystal prepared by slow evaporation of the solvent. From photoconductive measurement, nanorod stacks show a significant photosensitivity (354.57 µA/W) on par with bulk crystal (417.14 µA/W). These results suggest dibenzotetrathiafulvalene-tetracyanoquinodimethane (DBTTF-TCNQ) nanorods have a favorable crystal structure for carrier transport due to the difference of molecular stacking assembly.

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.

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.

Thermal Stability of Oxidized Single-Walled Carbon Nanotubes: Competitive Elimination and Decomposition Reaction Depending on the Degree of Functionalization.

The thermal stability of oxidized single-walled carbon nanotubes (SWNTs) with various degrees of oxidation was investigated. The oxidized SWNTs exhibited lower absorption and radial breathing mode (RBM) peaks and a higher intensity ratio of the D band to the G band (D/G) in their absorption and Raman spectra than those of the pristine SWNTs. After the thermal treatment, the D/G ratio of the oxidized SWNTs almost recovered its original intensity, regardless of the degree of oxidation. The absorption, photoluminescence (PL), and RBM peaks could not recover their original intensities when the oxidation degree was high. The results indicate that the elimination and decomposition reactions proceeded competitively depending on the degree of oxidation. In addition, a new PL peak was observed in the near-infrared region, and the PL peak intensity increased with the subsequent thermal treatment. The theoretical calculations provided an insight into the possible pathways for the decomposition of oxidized SWNTs, showing that the O2 elimination and CO/CO2 evolution proceed competitively during thermal treatment.

Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated.

Enhanced Immunostimulating Activity of Lactobacilli-Mimicking Materials by Controlling Size.

The design and synthesis of materials capable of activating the immune system in a safe manner is of great interest in immunology and related fields. Lactobacilli activate the innate immune system of a host when acting as probiotics. Here, we constructed lactobacilli-mimicking materials in which polysaccharide-peptidoglycan complexes (PS-PGs) derived from lactobacilli were covalently conjugated to the surfaces of polymeric microparticles with a wide variety of sizes, ranging from 200 nm to 3 µm. The artificial lactobacilli successfully stimulated macrophages without cytotoxicity. Importantly, we found that the size of artificial lactobacilli strongly influenced their immunostimulating activities, and that artificial lactobacilli of 1 µm exhibited 10-fold higher activity than natural lactobacilli. One major advantage of the artificial lactobacilli is facile control of size, which cannot be changed in natural lactobacilli. These findings provide new insights into the design of materials for immunology as well as the molecular biology of lactobacillus.

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).

Synthesis and immunestimulating activity of lactobacilli-originated polysaccharide-polymeric microparticle conjugates.

The design and synthesis of biomaterials capable of activating the immune system are of interest in immunology-related fields because of their ability to tune up the immune defenses of the host. Lactobacilli are a major constituent of normal human indigenous flora, and some specific strains are known to activate the immune system of the host as probiotics. In this study, we first fabricated novel biohybrid materials in which lactobacilli (L. casei strain Shirota, LcS)-originated polysaccharide-peptidoglycan complexes (PS-PGs) are conjugated with polymeric microparticles (MPs). PS-PGs conjugated onto polymeric MPs surfaces bound its specific antibody, suggesting that PS-PGs kept their original molecular recognition ability. The PS-PGs-based hybrid MPs with an appropriate density of conjugated PS-PGs effectively induced high levels of IL-12 production from macrophages without cytotoxicity. These results suggest that LcS-originated PS-PGs could be available bio-originated materials for developing novel biomaterials capable of activating the immune system in a safe manner.

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.

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.