Thermally Reversible Aggregation of Gold Nanoparticles in Polymer Nanocomposites through Hydrogen Bonding

The ability to tune the state of dispersion or aggregation of nanoparticles within polymer-based nanocomposites, through variations in the chemical and physical interactions with the polymer matrix, is desirable for the design of materials with switchable properties. In this study, we introduce a simple and effective means of reversibly controlling the association state of nanoparticles based on the thermal sensitivity of hydrogen bonds between the nanoparticle ligands and the matrix. Strong hydrogen bonding interactions provide excellent dispersion of gold nanoparticles functionalized with poly­(styrene-<i>r</i>-2-vinylpyridine) [P­(S-<i>r</i>-2VP)] ligands in a poly­(styrene-<i>r</i>-4-vinyl phenol) [P­(S-<i>r</i>-4VPh)] matrix. However, annealing at higher temperatures diminishes the strength of these hydrogen bonds, driving the nanoparticles to aggregate. This behavior is largely reversible upon annealing at reduced temperature with redispersion occurring on a time-scale of ∼30 min for samples annealed 50 °C above the glass transition temperature of the matrix. Using ultraviolet–visible absorption spectroscopy (UV–vis) and transmission electron microscopy (TEM), we have established the reversibility of aggregation and redispersion through multiple cycles of heating and cooling

Structural Characteristics of Amphiphilic Cyclic and Linear Block Copolymer Micelles in Aqueous Solutions

The structural characteristics of aqueous micelles composed of amphiphilic cyclic poly­(<i>n</i>-butyl acrylate-<i>b</i>-ethylene oxide) (cyclic PBA-<i>b</i>-PEO) or a linear analogue (i.e., linear poly­(<i>n</i>-butyl acrylate-<i>b</i>-ethylene oxide-<i>b</i>-<i>n</i>-butyl acrylate) (linear PBA-<i>b</i>-PEO-<i>b</i>-PBA)) were examined for the first time using synchrotron X-ray scattering techniques and quantitative data analysis. The scattering data were analyzed using a variety of methodologies in a comprehensive complementary manner. These analyses provided details of the structural information about the micelles. Both micelles were found to consist of a core and a fuzzy shell; however, the cyclic block copolymer had a strong tendency to form micelles with core and shell parts that were more compact and dense than the corresponding parts of the linear block copolymer micelles. The PBA block of the cyclic copolymer was found to form a hydrophobic core with a density that exceeded the density of the homopolymer in the bulk state. The structural differences originated primarily from the topological difference between the cyclic and linear block copolymers. The elimination of the chain end groups (which introduced entropy and increased the excess excluded volume) from the amphiphilic block copolymer yielded more stable dense micelles in solution

In-Situ Grazing Incidence Small-Angle X-ray Scattering Studies on Nanopore Evolution in Low-<i>k</i> Organosilicate Dielectric Thin Films

The first in-situ two-dimensional grazing incidence small-angle X-ray scattering (2D GISAXS) study on the evolution of nanopores during the thin film formation of porous dielectrics from composite films is reported. A soluble poly(methylsilsesquioxane) (PMSSQ) precursor and a four-armed poly(ε-caprolactone) (PCL4) were chosen as the model matrix and porogen components within the composite film. The measured 2D GISAXS data were analyzed quantitatively using a GISAXS formula derived under the distorted wave Born approximation. It is shown that in-situ GISAXS is a powerful tool for monitoring the evolution of nanopores in dielectric thin films, providing structural characteristics such as size, size distribution, shape, electron density, and porosity, all as a function of temperature and time. In addition, the mechanism for forming imprinted nanopores in the dielectric films by sacrificial thermal degradation of the porogen was determined by in-situ GISAXS analysis. Phase separation of the PCL4 porogen was induced below 200 °C by cross-linking of the PMSSQ precursor matrix during thermal curing. This process generated porogen aggregates, each individually imprinted pore in the film through thermal degradation; the shape, size, and size distribution of the porogen aggregates are directly reflected in the dimensions of the imprinted pores. Moreover, it was found that higher porogen loadings caused larger porogen aggregates with a greater size distribution. The present results thus show that the structural characteristics of nanopores imprinted within PMSSQ dielectric films are governed by the PCL4 porogen aggregates formed through curing of the PMSSQ precursor matrix

Alternating Copolymers Containing Bithiophene and Dialkoxynaphthalene for the Applications to Field Effect Transistor and Photovoltaic Cell: Performance and Stability

Poly(5′,5′′-bithiophene-alt-2,6-[(1,5-didecyloxy)naphthalene]) (PBDN) was synthesized from 2,6-dibromo-l,5-didecyloxynaphthalene and 1,1′-[2,2′-bithiophene]-5,5′-diylbis[1,1,1-trimethylstannane] and was used as the active layer in organic thin-film transistors (OTFTs) and organic photovoltaic cells (OPVs). The obtained PBDN was soluble in organic solvents such as chloroform, chlorobenzene, and toluene and had a weight-averaged molecular weight of 9100, with a polydispersity index of 1.31. The photoluminescence (PL) maximum of the polymer was found at 500 and 530 nm in solution and at 567 nm in the film state, respectively. The highest occupied molecular orbital (HOMO) level of PBDN was low (−5.38 eV, ultraviolet photoemission spectroscopy and cyclic voltammetry), and the solution-processed thin-film transistors (TFTs) prepared using this polymer only showed a minimal change in their performance (2/(V s). This excellent air stability is superior to those of other solution-processed polymer-based OTFTs. Analysis of the thin-film structure by in situ grazing-incidence X-ray diffraction, near-edge X-ray absorption fine structure spectroscopy, and atomic force microscopy showed that not only the low HOMO level of PBDN but also the presence of close-packed frustrated structures in the polymer film were responsible for the superior stability of the devices. Photovoltaic performances of PBDN were also presented with a high open circuit voltage of 0.83 V and power conversion efficiency of 1.3% when blended with [6,6]-phenyl-C61-butyric acid methyl ester

Reusable, Ultrasensitive, Patterned Conjugated Polyelectrolyte–Surfactant Complex Film with a Wide Detection Range for Copper Ion Detection

Conjugated polyelectrolytes (CPEs) are emerging as promising materials in the sensor field because they enable high-sensitivity detection of various substances in aqueous media. However, most CPE-based sensors have serious problems in real-world application because the sensor system is operated only when the CPE is dissolved in aqueous media. Here, the fabrication and performance of a water-swellable (WS) CPE-based sensor driven in the solid state are demonstrated. The WS CPE films are prepared by immersing a water-soluble CPE film in cationic surfactants of different alkyl chain lengths in a chloroform solution. The prepared film exhibits rapid, limited water swellability despite the absence of chemical crosslinking. The water swellability of the film enables the highly sensitive and selective detection of Cu2+ in water. The fluorescence quenching constant and the detection limit of the film are 7.24 × 106 L mol–1 and 4.38 nM (0.278 ppb), respectively. Moreover, the film is reusable via a facile treatment. Furthermore, various fluorescent patterns introduced by different surfactants are successfully fabricated by a simple stamping method. By integrating the patterns, Cu2+ detection in a wide concentration range (nM–mM) can be achieved

Reusable, Ultrasensitive, Patterned Conjugated Polyelectrolyte–Surfactant Complex Film with a Wide Detection Range for Copper Ion Detection

Conjugated polyelectrolytes (CPEs) are emerging as promising materials in the sensor field because they enable high-sensitivity detection of various substances in aqueous media. However, most CPE-based sensors have serious problems in real-world application because the sensor system is operated only when the CPE is dissolved in aqueous media. Here, the fabrication and performance of a water-swellable (WS) CPE-based sensor driven in the solid state are demonstrated. The WS CPE films are prepared by immersing a water-soluble CPE film in cationic surfactants of different alkyl chain lengths in a chloroform solution. The prepared film exhibits rapid, limited water swellability despite the absence of chemical crosslinking. The water swellability of the film enables the highly sensitive and selective detection of Cu2+ in water. The fluorescence quenching constant and the detection limit of the film are 7.24 × 106 L mol–1 and 4.38 nM (0.278 ppb), respectively. Moreover, the film is reusable via a facile treatment. Furthermore, various fluorescent patterns introduced by different surfactants are successfully fabricated by a simple stamping method. By integrating the patterns, Cu2+ detection in a wide concentration range (nM–mM) can be achieved

Reusable, Ultrasensitive, Patterned Conjugated Polyelectrolyte–Surfactant Complex Film with a Wide Detection Range for Copper Ion Detection

Conjugated polyelectrolytes (CPEs) are emerging as promising materials in the sensor field because they enable high-sensitivity detection of various substances in aqueous media. However, most CPE-based sensors have serious problems in real-world application because the sensor system is operated only when the CPE is dissolved in aqueous media. Here, the fabrication and performance of a water-swellable (WS) CPE-based sensor driven in the solid state are demonstrated. The WS CPE films are prepared by immersing a water-soluble CPE film in cationic surfactants of different alkyl chain lengths in a chloroform solution. The prepared film exhibits rapid, limited water swellability despite the absence of chemical crosslinking. The water swellability of the film enables the highly sensitive and selective detection of Cu2+ in water. The fluorescence quenching constant and the detection limit of the film are 7.24 × 106 L mol–1 and 4.38 nM (0.278 ppb), respectively. Moreover, the film is reusable via a facile treatment. Furthermore, various fluorescent patterns introduced by different surfactants are successfully fabricated by a simple stamping method. By integrating the patterns, Cu2+ detection in a wide concentration range (nM–mM) can be achieved

Reusable, Ultrasensitive, Patterned Conjugated Polyelectrolyte–Surfactant Complex Film with a Wide Detection Range for Copper Ion Detection

Conjugated polyelectrolytes (CPEs) are emerging as promising materials in the sensor field because they enable high-sensitivity detection of various substances in aqueous media. However, most CPE-based sensors have serious problems in real-world application because the sensor system is operated only when the CPE is dissolved in aqueous media. Here, the fabrication and performance of a water-swellable (WS) CPE-based sensor driven in the solid state are demonstrated. The WS CPE films are prepared by immersing a water-soluble CPE film in cationic surfactants of different alkyl chain lengths in a chloroform solution. The prepared film exhibits rapid, limited water swellability despite the absence of chemical crosslinking. The water swellability of the film enables the highly sensitive and selective detection of Cu2+ in water. The fluorescence quenching constant and the detection limit of the film are 7.24 × 106 L mol–1 and 4.38 nM (0.278 ppb), respectively. Moreover, the film is reusable via a facile treatment. Furthermore, various fluorescent patterns introduced by different surfactants are successfully fabricated by a simple stamping method. By integrating the patterns, Cu2+ detection in a wide concentration range (nM–mM) can be achieved