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Well-defined nanostructures composed of conjugated polymers have attracted significant attention due to their intriguing electronic and optical properties. However, precise control of the size and uniformity of these semiconducting nanostructures is still rare and challenging, despite recent advances in strategies to obtain self-assembled nanostructures with narrow dispersions. Herein, we demonstrate the preparation of fluorescent conjugated block copolymers by one-shot polymerization and rapid formation of nanofibers in a few minutes via light-induced crystallization-driven self-assembly, driven by facile cis-to- trans photoisomerization of its poly( p-phenylenevinylene) blocks. Furthermore, living self-assembly was possible, allowing not only nanofibers with excellent length control and narrow size distribution but also ABA triblock comicelles and gradient comicelles, to be produced by seeded growth. Lastly, the seeded growth could be activated and deactivated repeatedly by switching the light on and off, analogous to light-induced living radical polymerization.

Here, we propose a simple mechanoresponsive system on patterned soft surfaces to manipulate both anisotropy and orientation of liquid wetting. On the poly(dimethylsiloxane) embedding line patterned structures, additional topographies, such as wrinkles and cracks, can be provided by applying compressive and tensile stress, respectively. This tunable hierarchy of structures with the different scales and directions of lines, wrinkles, and cracks allow the mechanoresponsive control of anisotropic wetting in a single platform. In addition, the wetting behavior on those surfaces is precisely investigated based on the concept of critical contact angle to overcome the ridges in a step flow.

Dye aggregation and electron recombination in TiO2 photoanodes are the two major phenomena lowering the energy conversion efficiency of dye-sensitized solar cells (DSCs). Herein, we introduce a novel surface modification strategy of TiO2 photoanodes by the fluorinated self-assembled monolayer (F-SAM) formation with 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFTS), blocking the vacant sites of the TiO2 surface after dye adsorption. The F-SAM helps to efficiently lower the surface tension, resulting in efficient repelling ions, e.g., I3(-), in the electrolyte to decrease the electron recombination rate, and the role of F-SAM is characterized in detail by impedance spectroscopy using a diffusion-recombination model. In addition, the dye aggregates on the TiO2 surface are relaxed by the F-SAM with large conformational perturbation (i.e., helix structure) seemingly because of steric hindrance developed during the SAM formation. Such multifunctional effects suppress the electron recombination as well as the intermolecular interactions of dye aggregates without the loss of adsorbed dyes, enhancing both the photocurrent density (11.9 → 13.5 mA cm(-2)) and open-circuit voltage (0.67 → 0.72 V). Moreover, the combined surface modification with the F-SAM and the classical coadsorbent further improves the photovoltaic performance in DSCs.

Poly[sulfur-random-1,3-diisopropenylbenzene (DIB)] copolymers synthesized via inverse vulcanization form electrochemically active polymers used as cathodes for high-energy density Li-S batteries, capable of enhanced capacity retention (1005 mAh/g at 100 cycles) and lifetimes of over 500 cycles. In this prospective, we demonstrate how analytical electron microscopy can be employed as a powerful tool to explore the origins of the enhanced capacity retention. We analyze morphological and compositional features when the copolymers, with DIB contents up to 50% by mass, are blended with carbon nanoparticles. Replacing the elemental sulfur with the copolymers improves the compatibility and interfacial contact between active sulfur compounds and conductive carbons. There also appears to be improvements of the cathode mechanical stability that leads to less cracking but preserving porosity. This compatibilization scheme through stabilized organosulfur copolymers represents an alternative strategy to the nanoscale encapsulation schemes which are often used to improve the cycle life in high-energy density Li-S batteries.

We report on dynamic covalent polymers derived from elemental sulfur that can be used as thermally healable optical polymers for mid-IR thermal imaging applications. By accessing dynamic S–S bonds in these sulfur copolymers, surface scratches and defects of free-standing films of poly(sulfur-random-1,3-diisopropenylbenzene) (poly(S-r-DIB) can be thermally healed, which enables damaged lenses and windows from these materials to be reprocessed to recover their IR imaging performance. Correlation of the mechanical properties of these sulfur copolymers with different curing methods provided insights to reprocess damaged samples of these materials. Mid-IR thermal imaging experiments with windows before and after healing of surface defects demonstrated successful application of these materials to create a new class of “scratch and heal” optical polymers. The use of dynamic covalent polymers as healable materials for IR applications offers a unique advantage over the current state of the art (e.g., germanium or ...

Dye-sensitized solar cells equipped with cationic and neutral RuII-based sensitizers [Ru(ddpd){tpy(COOH)3}]2+ [12+; ddpd = N,N′-dimethyl-N,N′-di(pyridin-2-yl)pyridin-2,6-diamine, tpy(COOH)3 = 2,2″6′,2″-terpyridine-4,4′,4″-tricarboxylic acid] and [Ru(ddpd){tpy(COOH)(COO)2}] (2) with and without the coadsorbent chenodeoxycholic acid were constructed with I3–/I– or the CoIII/II-based redox mediators [Co(bpy)3]3+/2+ (33+/2+; bpy = 2,2′-bipyridine) and [Co(ddpd)2]3+/2+ (43+/2+) in the presence of LiClO4 and 4-tert-butylpyridine. The best photovoltaic performance was achieved by using the 43+/2+ shuttle and the neutral sensitizer 2 without coadsorbent. The higher short-circuit photocurrent density and higher electron recombination lifetimes obtained with this combination suggest slow electron recombination kinetics at the TiO2 surface with the CoIII complex 43+. The slow electron transfer to 43+ is tentatively ascribed to the high-lying π* orbitals of the electron-rich ddpd ligands, which result in a weak electronic coupling. This contrasts with the faster recombination with 33+, which features the low-energy π* orbitals of the bpy ligands.

To realize the full-color displays using colloidal nanocrystal quantum dot (QD)-based light emitting diodes (QLEDs), the emissive QD layer should be patterned to red (R), green (G), and blue (B) subpixels on a micrometer scale by the solution process. Here, we introduced a soft contact QD-transplanting technique onto the vacuum-deposited small molecules without pressure to pattern the QD layer without any damage to the prior organic layers. We examined the patternability of QDs by studying the surface properties of various organic layers systematically. As a result, we found that the vacuum-deposited 4,4',4″-tri(N-carbazolyl)triphenylamine (TCTA) layer is suitable for QD-transplanting. A uniform and homogeneous QD patterns down to 2 μm could be formed for all the RGB QDs (CdSe/CdS/ZnS, CdSe@ZnS, and Cd1-xZnxS@ZnS, respectively) with this method. Finally, we demonstrated the R, G, and B QLEDs by transplanting each QD onto the soft TCTA layer, exhibiting higher brightness (2497, 14 102, and 265 cd m(-2), respectively) and efficiency (1.83, 8.07, and 0.19 cd A(-1), respectively) than those of the previous QLEDs fabricated by other patterning methods. Because this pressure-free technique is essential for patterning and stacking the QDs onto the soft organic layer, we believe that both fundamental study and the engineering approach presented here are meaningful for the realization of the colloidal QD-based full-color displays and other optoelectronic devices.

Many natural materials are complex composites whose mechanical properties are often outstanding considering the weak constituents from which they are assembled. Nacre, made of inorganic (CaCO 3 ) and organic constituents, is a textbook example because of its strength and toughness, which are related to its hierarchical structure and its well-defi ned organic–inorganic interface. Emulating the construction principles of nacre using simple inorganic materials and polymers is essential for understanding how chemical composition and structure determine biomaterial functions. A hard multilayered nanocomposite is assembled based on alternating layers of TiO 2 nanoparticles and a 3-hydroxytyramine (DOPA) substituted polymer (DOPA-polymer), strongly cemented together by chelation through infi ltration of the polymer into the TiO 2 mesocrystal. With a Young’s modulus of 17.5 ± 2.5 GPa and a hardness of 1.1 ± 0.3 GPa the resulting material exhibits high resistance against elastic as well as plastic deformation. A key feature leading to the high strength is the strong adhesion of the DOPA-polymer to the TiO 2 nanoparticles.

Emission wavelength control in fluorescent nanoparticles (NPs) is crucial for their applications. In the case of inorganic quantum dots or dye-impregnated silica NPs, such a control is readily achieved by changing the size of the particles or choosing appropriate fluorescent dyes, respectively. A similar modular approach for controlling the emission wavelength of fluo-rescent polymer NPs, however, is difficult. This article reports on fluorescent polymer NPs, the synthesis of which provides a platform for a modular approach towards the preparation of fluorescent NPs of desired emission wavelength. Atom-transfer radical polymerization (ATRP) is employed to synthesize reactive ester polymers, which are then easily modified with a commercially available dye and subsequently subjected to nanoprecipitation. The resulting NPs, with low size polydispersity, show an enhanced emission quantum yield when compared with the same dye molecules in solution.

Directional wetting or spreading on asymmetric structures have received much attention because of their potential to control the liquid flow in microfluidic devices. Although there have been many reports on directional liquid flows, the flow speeds of the directional flows could not be predicted. Here, we present a controllable strategy for directional flow on a multiscale two-face prism array, one face is smooth and the other face is roughened. The polymeric surface of the prism is roughened by oxygen plasma while the other side is blocked by a coated metal film. With the designed structure, we demonstrate a unidirectional liquid flow and manipulate the flow speed in an open channel. From a simplified model suggested here, the flow speed could be predicted quantitatively.

Elementarer Schwefel ist ein weitverbreitetes und preiswertes Material, das bei der Erdgas- und Erdol-Raffination als Nebenprodukt anfallt. Die Notwendigkeit, neue Energiespeichersysteme zu entwickeln, brachte vor kurzem das Potential von Schwefel als hochleistungsfahiges Kathodenmaterial in Sekundarbatterien ans Licht. Auserdem wurden die nutzlichen optischen Eigenschaften schwefelhaltiger Materialien im Infrarotbereich entdeckt. Diese Entwicklungen gepaart mit den wachsenden okologischen Bedenken im Zusammenhang mit der globalen Produktion von uberschussigem elementarem Schwefel fuhrten zu einem grosen Interesse an seiner Nutzung als Rohstoff in Werkstoffanwendungen. Dieser Kurzaufsatz konzentriert sich auf die jungsten Entwicklungen physikalischer und chemischer Methoden fur die direkte Verarbeitung von elementarem Schwefel in der Produktion funktionaler Verbundwerkstoffe und Polymere.

The synthesis of polymeric materials using elemental sulfur (S8) as the chemical feedstock has recently been developed using a process termed inverse vulcanization. The preparation of chemically stable sulfur copolymers was previously prepared by the inverse vulcanization of S8 and 1,3-diisopropenylbenzene (DIB); however, the development of synthetic methods to introduce new chemical functionality into this novel class of polymers remains an important challenge. In this report the introduction of polythiophene segments into poly(sulfur-random-1,3-diisopropenylbenzene) is achieved by the inverse vulcanization of S8 with a styrenic functional 3,4-propylenedioxythiophene (ProDOT-Sty) and DIB, followed by electropolymerization of ProDOT side chains. This methodology demonstrates for the first time a facile approach to introduce new functionality into sulfur and high sulfur content polymers, while specifically enhancing the charge conductivity of these intrinsically highly resistive materials.

Although strong and stiff synthetic composites have long been developed, the microstructure of today's most advanced composites has yet to achieve the sophisticated hierarchy of hybrid materials built up by living organisms. We have assembled hard and tough multilayered nanocomposites, which contain alternating layers of Fe3O4 nanoparticles and a 3-hydroxy-tyramine (dopamine) substituted polymer (dopamine modified polymer), strongly cemented together by chelation through infiltration of the polymer into the Fe3O4 mesocrystal. With a Young's modulus of 17 ± 3 GPa and a hardness of 1.3 ± 0.4 GPa the nanocomposite exhibits high resistance against elastic as well as plastic deformation. Key features leading to the high strength are the strong adhesion of the polymer to the inorganic nanoparticles and the layered assembly.

Oligomeric, hydrophobic coadsorbents based on polystyrene (o-PS, Mn = 2600) terminated by a carboxylic acid exhibit dual functions in dye-sensitized solar cells (DSCs): suppression of electron recombination at the TiO2 surface, and enhanced concentration of the strongly-anchored dye, N719, which has two carboxylic acid groups. Engineering the TiO2 surface via o-PS results in the concurrent and significant enhancement of photovoltage and photocurrent, consequently increasing the energy conversion efficiency of DSCs by as much as 28.7%. The electron recombination rate was largely reduced via the blockage of vacant sites with o-PS chains on the TiO2 surface due to the physical hindrance to I3−s in electrolyte. In addition, the formation of the o-PS:I2 charge transfer complex at the photoanode/electrolyte interface lessened the effective concentrations of free I3− and/or I2 for electron recombination. Upon sequential o-PS coadsorption, the concentration of the strongly-anchored dyes on the TiO2 surface was increased via deprotonation of the weakly-anchored dyes, giving rise to an increase in the electron injection efficiency and, subsequently, the overall power conversion efficiency. The dual functions of the o-PS coadsorbent have been therefore demonstrated to increase the overall efficiency of DSCs.

High sulfur content copolymers were prepared via inverse vulcanization of sulfur with 1,4-diphenylbutadiyne (DiPhDY) for use as the active cathode material in lithium–sulfur batteries. These sulfur-rich polymers exhibited excellent capacity retention (800 mA h g−1 at 300 cycles) and extended battery lifetimes of over 850 cycles at C/5 rate.

The use of preformed inorganic nanoparticles as “colloidal monomers” has received recent attention for the formation of one-dimensional (1-D) mesostructures, or “colloidal polymers.” These colloidal monomers form linear assemblies through attractive, directional, interparticle interactions, which are similar to covalent or supramolecular interactions in classical polymer science. However, in contrast to the high degree of structural control available in the synthesis of classical molecular polymers, methods to control fundamental structural features such as chain length (DP), composition (copolymers), and architecture (linear, branched, etc.) are still being developed for NP-based colloidal polymer systems. We therefore review the colloidal polymerization of inorganic nanoparticle monomers by applying the conceptual framework provided by polymer science to categorize these novel systems. The descriptive nomenclature used for classical polymers is applied to NP assembly to define more explicitly the types of colloidal polymers formed in terms of DP, architecture, and composition (for binary NP assemblies). This review includes descriptions of inorganic nanoparticle types useful for the formation of colloidal polymers with examples chosen to demonstrate control over mesoscopic structure and composition. The various emergent optical, electrical and electrochemical properties from these materials are also reviewed and correlated with structural control achieved in various colloidal polymer systems.

Herein, we report unique features of the assemblies of tetrapod-shaped colloidal nanocrystals (TpNCs) with lengthy arms applicable to flexible thin-film transistors. Due to the extended nature of tetrapod geometry, films made of the TpNC assemblies require reduced numbers of inter-NC hopping for the transport of charge carriers along a given channel length; thus, enhanced conductivity can be achieved compared to those made of typical spherical NCs without arms. Moreover, electrical conduction through the assemblies is tolerant against mechanical bending because interconnections between TpNCs can be well-preserved under bending. Interestingly, both the conductivity of the assemblies and their mechanical tolerance against bending are improved with an increase in the length of tetrapod arms. The arm length-dependency was demonstrated in a series of CdSe TpNC assemblies with different arm lengths (l = 0-90 nm), whose electrical conduction was modulated through electrolyte gating. From the TpNCs with the longest arm length included in the study (l = 90 nm), the film conductivity as high as 20 S/cm was attained at 3 V of gate voltage, corresponding to electron mobility of10 cm

The synthesis of dynamic covalent polymers with controllable amounts of sulfur–sulfur (S–S) bonds in the polymer backbone via inverse vulcanization of elemental sulfur (S8) and 1,3-diisopropenylbenzene (DIB) is reported. An attractive feature of the inverse vulcanization process is the ability to control the number and dynamic nature of S–S bonds in poly(sulfur-random-(1,3-diisopropenylbenzene)) (poly(S-r-DIB) copolymers by simple variation of S8/DIB feed ratios in the copolymerization. S–S bonds in poly(S-r-DIB) copolymers of high sulfur content and sulfur rank were found to be more dynamic upon exposure to either heat, or mechanical stimuli. Interrogation of dynamic S–S bonds was conducted in the solid-state utilizing electron paramagnetic resonance spectroscopy and in situ rheological measurements. Time-dependent rheological property behavior demonstrated a compositional dependence of the healing behavior in the copolymers, with the highest sulfur (80 wt % sulfur) content affording the most rapid dynam...

We report transparent Al:LiF composite/molybdenum oxides (MoO3) as interconnecting layers for tandem white organic light emitting diodes (WOLEDs) consisting of blue and red phosphorescent unit devices. The Al:LiF (3 nm)/MoO3 (10 nm) interconnecting layers show a high transmittance, good carrier generation and injection capability for tandem WOLEDs. The performance of tandem WOLEDs is sensitive to the LiF doping concentration, which is mainly attributed to the difference in efficiency of carrier injection into the adjoining electroluminescent units. For 10~20% LiF concentration, the external quantum efficiency of tandem device is almost equal to the sum of the efficiencies of blue and red OLEDs at high current density; furthermore, a small variation of Commission Internationale de l'Eclairage (CIE) coordinates with the current density is obtained.

The synthesis of high content sulfur copolymers via the inverse vulcanization of elemental sulfur and 1,3-diisopropenylbenzene (DIB) on a one-kilogram scale is reported in a single step process. Investigation into the effects of temperature, reaction scale, and comonomer feed ratios on the inverse vulcanization process of S8 and DIB were explored to suppress the Trommsdorf effect and enable large scale synthesis of these copolymers. The copolymers were then successfully used as the active cathode materials in Li-S batteries, exhibiting enhanced capacity retention and battery lifetimes (608 mAh/g at 640 cycles) at a C/10 rate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 173–177

Water-repelling surfaces inspired by lotus leaves have been developed for their commercial needs in superhydrophobic and self-cleaning coatings on glasses and windows. The extraordinary properties originate from their multiscale structures with waxy materials. To obtain high transparency as well as superhydrophobicity, microhair arrays are designed with large spacing to reduce optical scattering effects caused by microstructures, but with a trilevel hierarchical structure to compensate for the loss of superhydrophobicity. In this study, a soft molding technique on wet pastes consisting of nanoparticles (NPs) is proposed to create a multilevel hierarchical structure of sub-100 nm nanoparticles, which demonstrates excellent water repellency. Additionally, full advantage is taken of the TiO2 NP mesoporous structure for UV protection and for its ability to attach to various kinds of functional (for example, photoresponsive) dyes. Furthermore, the stability of fluorinated surfaces against UV light is enhanced by the passivation of the TiO2 surface with a thin silica coating.

Stable push-pull substituted heteroleptic bis(tridentate) ruthenium(II) polypyridine complexes with COOH or 2,2′-bipyridine anchor groups have been prepared and characterized by 1H, 13C and 15N NMR 1D and 2D spectroscopy, infrared spectroscopy, elemental analysis, high-resolution ESI mass spectrometry, electrochemistry, UV/Vis absorption spectroscopy, luminescence spectroscopy, and density functional calculations. The complexes feature a pronounced electronic directionality and high absorption wavelengths up to λmax = 544 nm extending to 720 nm as a result of favorable push-pull substitutions. A remarkable photostability in the presence of water and coordinating ions (I–) was discovered for the tridentate complexes when compared with the standard ruthenium sensitizer N719 and tris(bidentate) [Ru(bpy)3](PF6)2, which are highly photolabile under the same conditions (photodissociation/photosubstitution). The complexes were studied as photosensitizers in dye-sensitized solar cells. The incident photon-to-current conversion efficiency follows the absorption spectra into the NIR region. However, the high positive charge of the complexes (2+) favors the recombination of the injected electrons with I3– of the redox electrolyte, which is evidenced by high dark currents and short electron recombination lifetimes, leading to low cell performances compared with cells with the negatively charged N719 dye.

The synthesis of a modular colloidal polymer system based on the dipolar assembly of CdSe@CdS nanorods functionalized with a single cobalt nanoparticle "tip" (CoNP-tip) is reported. These heterostructured nanorods spontaneously self-assembled via magnetic dipolar associations of the cobalt domains. In these assemblies, CdSe@CdS nanorods were carried as densely grafted side chain groups along the dipolar NP chain to form bottlebrush-type colloidal polymers. Nanorod side chains strongly affected the conformation of individual colloidal polymer bottlebrush chains and the morphology of thin films. Dipolar CoNP-tipped nanorods were then used as "colloidal monomers" to form mesoscopic assemblies reminiscent of traditional copolymers possessing segmented and statistical compositions. Investigation of the phase behavior of colloidal polymer blends revealed the formation of mesoscopic phase separated morphologies from segmented colloidal copolymers. These studies demonstrated the ability to control colloidal polymer composition and morphology in a manner observed for classical polymer systems by synthetic control of heterostructured nanorod structure and harnessing interparticle dipolar associations.

Polymers for IR imaging: The preparation of high refractive index polymers (n = 1.75 to 1.86) via the inverse vulcanization of elemental sulfur is reported. High quality imaging in the near (1.5 μm) and mid-IR (3-5 μm) regions using high refractive index polymeric lenses from these sulfur materials was demonstrated.

Sulfur-rich copolymers based on poly(sulfur-random-1,3-diisopropenylbenzene) (poly(S-r-DIB)) were synthesized via inverse vulcanization to create cathode materials for lithium–sulfur battery applications. These materials exhibit enhanced capacity retention (1005 mAh/g at 100 cycles) and battery lifetimes over 500 cycles at a C/10 rate. These poly(S-r-DIB) copolymers represent a new class of polymeric electrode materials that exhibit one of the highest charge capacities reported, particularly after extended charge–discharge cycling in Li–S batteries.

We demonstrate the modular fabrication of nanocrystal/polymer hybrid bulk heterojunction solar cells based on breakwater-like CdSe tetrapod (TP) nanocrystal networks infused with poly(3-hexylthiophene) (P3HT). This fabrication method consists of sequential steps for forming the hybrid active layers: the assembly of a breakwater-like CdSe TP network followed by nanocrystal surface modification and the infusion of semiconducting polymers. Such a modular approach enables the independent control of the nanoscopic morphology and surface chemistry of the nanocrystals, which are generally known to exhibit complex correlations, in a reproducible manner. Using these devices, the influence of the passivation ligands on solar cell characteristics could be clarified from temperature-dependent solar cell experiments. We found that a 2-fold increase in the short-circuit current with 1-hexylamine ligands, compared with the value based on pyridine ligands, originates from the reduced depth of trap states, minimizing the ...

We demonstrate QLEDs implementing wider active layers (50 nm) based on QD–conducting polymer nanohybrids, which exhibit a stable operational device performance across a wide range of current densities and brightness. A comparative study reveals that the significant suppression of efficiency roll-off in the high current density regime is primarily attributed to a sufficient charge carrier distribution over the wider active layer and improved charge carrier balance within QDs enabled by the hybridization of QDs with conducting polymers. Utilization of this finding in future studies should greatly facilitate the development of high performance, stable QLEDs at high current density or luminance regime toward displays or solid-state lighting applications.

The synthesis of a ferromagnetic heterostructured material consisting of a CdSe@CdS nanorod attached to a single dipolar cobalt nanoparticle (CoNP) into a “matchstick” morphology is reported. CdSe@CdS nanorods were modified by an activation reaction with Pt(acac)2 which enabled selective one-sided deposition of a dipolar metallic CoNP-tip via the thermolysis of Co2(CO)8 in the presence of polystyrene ligands. Small (

We present multifunctional dendrimer ligands that serve as the charge injection controlling layer as well as the adhesive layer at the interfaces between quantum dots (QDs) and the electron transport layer (ETL) in quantum dot light-emitting diodes (QLEDs). Specifically, we use primary amine-functionalized dendrimer ligands (e.g., a series of poly(amidoamine) dendrimers (PADs, also referred to PAMAM)) that bind to the surface of QDs by replacing the native ligands (oleic acids) and also to the surface of ZnO ETL. PAD ligands control the electron injection rate from ZnO ETL into QDs by altering the electronic energy levels of the surface of ZnO ETL and thereby improve the charge balance within QDs in devices, leading to the enhancement of the device efficiency. As an ultimate achievement, the device efficiency (peak external quantum efficiency) improves by a factor of 3 by replacing the native ligands (3.86%) with PAD ligands (11.36%). In addition, multibranched dendrimer ligands keep the QD emissive layer intact during subsequent solution processing, enabling us to accomplish solution-processed QLEDs. The approach and results in the present study emphasize the importance of controlling the ligands of QDs to enhance QLED performance and also offer simple yet effective chemical mean toward all-solution-processed QLEDs.

Understanding the self-assembly process of amyloid nanofibrils is important in protein engineering for their potential uses in material sciences and medical applications. Here, we investigated the nanomechanical properties and structures of κ-casein nanofibrils during thermally induced amyloidogenesis. After treatment with dithiothreitol to reduce disulfide bonds, κ-casein from bovine milk was incubated at various temperatures from 37 to 95 °C. Twisted mature nanofibrils were only obtained at high thermal energies of 95 °C with fast growth kinetics. Nanomechanical studies using atomic force microscopy show the highest Young's moduli (2.6 ± 0.4 GPa) for mature fibrils when compared to those of oligomers and protofibrils (0.6 ± 0.1 and 2.2 ± 0.3 GPa, respectively). These enhanced mechanical properties are mainly attributed to the twisted cores of the mature fibrils containing β-sheet stacks. Amyloidogenesis of κ-casein is highly dependent on the magnitude of thermal energy, determining both the types and shapes of the nanofibrils and their different mechanical properties.

Despite their unparalleled theoretical capacity, lithium‐metal anodes suffer from well‐ known indiscriminate dendrite growth and parasitic surface reactions. Conductive scaffolds with lithium uptake capacity are recently highlighted as promising lithium hosts, and carbon nanotubes (CNTs) are an ideal candidate for this purpose because of their capability of percolating a conductive network. However, CNT networks are prone to rupture easily due to a large tensile stress generated during lithium uptake– release cycles. Herein, CNT networks integrated with a polyrotaxane‐incorporated poly(acrylic acid) (PRPAA) binder via supramolecular interactions are reported, in which the ring‐sliding motion of the polyrotaxanes endows extraordinary stretchability and elasticity to the entire binder network. In comparison to a control sample with inelastic binder (i.e., poly(vinyl alcohol)), the CNT network with PRPAA binder can endure a large stress during repeated lithium uptake–release cycles, thereby enhancing the mechanical integrity of the corresponding electrode over battery cycling. As a result, the PRPAA‐incorporated CNT network exhibits substantially improved cyclability in lithium–copper asymmetric cells and full cells paired with olivine‐LiFePO4, indicating that high elasticity enabled by mechanically interlocked molecules such as polyrotaxanes can be a useful concept in advancing lithium‐metal batteries.

We demonstrate the improvement in the efficiency of planar heterojunction perovskite solar cells by employing cadmium selenide tetrapods (CdSe TPs) as an electron extraction layer. The insertion of the CdSe TP layer between the titanium oxide (TiO2) and perovskite film facilitates electron transfer at the TiO2/perovskite interface, as indicated by the significantly quenched steady-state photoluminescence of the perovskite film. Furthermore, we observed a conductivity enhancement of the perovskite film by introducing the CdSe TP layer. The combination of both effects induced by the TPs leads to enhancement in the carrier extraction as well as decreased recombination losses in the perovskite solar cells. As a result, an efficiency of 13.5% (1 sun condition) is achieved in the perovskite solar cells that incorporate the CdSe TP layer, which is 10% higher than that of the device without the CdSe TP layer.

We report very efficient red, green, blue, and white light-emitting diodes based on colloidal quantum dots (QLEDs) using an inverted device architecture. We also review recent research progress of QLEDs and discuss issues for realizing full-color QLED displays.

Light-emitting electrochemical cells (LECs) with a simple device structure were prepared by using heteroleptic bis(tridentate) ruthenium(II) complexes [1](PF6)(2)-[3](PF6)(2) as emitters. The push-pull substitution shifts the emission energy to low energy, into the NIR region. The devices emit deep red light up to a maximum emission wavelength of 755 nm [CIE (International Commission on Illumination) coordinates: x = 0.731, y = 0.269 for [3](PF6)(2)], which, to the best of our knowledge, is the lowest emission energy for LECs containing bis(tridentate) ruthenium(II) complexes. A device structure of ITO/PEDOT:PSS/ruthenium(II) complex/Ag was used, and the thickness of the emitting layer was measured by AFM [ITO: indium tin oxide, PEDOT: poly(3,4-ethylenedioxythiophene), PSS: poly(styrenesulfonate), AFM: atomic force microscopy]. To enhance the external quantum efficiency (EQE), cells were fabricated with and without poly(methyl methacrylate) (PMMA) as additive in the emitting layer.

We investigate orientation and lateral ordering of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) diblock copolymer (diBCP) thin films placed on ordered nanoparticle (NP) monolayers. The densely packed NP monolayers were prepared on silicon substrates with the Langmuir–Blodgett (LB) deposition technique. The perpendicular domain orientation of BCP thin films is obtained on the ordered NP monolayers due to the nanoscale regular roughness which exerts the elastic deformation on the BCP nanodomains and suppresses the substrate-induced parallel orientation. The effect of BCP film thickness as well as the NP size on the orientation of BCP nanodomains was systematically investigated. We also demonstrate the defect-tolerant ordering of the perpendicular orientation of BCP thin films on the NP-vacant sites.

The therapeutic efficacy of drugs often depends on the drug delivery carrier. For efficient delivery of therapeutic proteins, delivery carriers should enable the loading of large doses, sustained release, and retention of the bioactivity of the therapeutic proteins. Here, it is demonstrated that graphene oxide (GO) is an efficient carrier for delivery of therapeutic proteins. Titanium (Ti) substrates are coated with GO through layer-by-layer assembly of positively (GO-NH₃⁺) and negatively (GO-COO⁻) charged GO sheets. Subsequently, a therapeutic protein (bone morphogenetic protein-2, BMP-2) is loaded on the GO-coated Ti substrate with the outermost coating layer of GO-COO⁻ (Ti/GO⁻). The GO coating on Ti substrate enables loading of large doses and the sustained release of BMP-2 with preservation of the structure and bioactivity of the drug. The extent of in vitro osteogenic differentiation of human bone marrow-derived mesenchymal stem cells is higher when they are cultured on Ti/GO- carrying BMP-2 than when they are cultured on Ti with BMP-2. Eight weeks after implantation in mouse models of calvarial defects, the Ti/GO-/BMP-2 implants show more robust new bone formation compared with Ti, Ti/GO-, or Ti/BMP-2 implants. Therefore, GO is an effective carrier for the controlled delivery of therapeutic proteins, such as BMP-2, which promotes osteointegration of orthopedic or dental Ti implants.

The synthesis and thermomechanical properties of a novel class of self-healing perfluoropolyethers (PFPEs) is reported. By decoration of 2-ureido-4[1H]-pyrimidone end groups on the termini of low molar mass PFPE, the formation of supramolecular polymers and networks held together via hydrogen bonding associations was achieved. These novel supramolecular polymer materials exhibit a combination of enhanced modulus and elasticity, along with self-healing properties, where rapid self-healing time was demonstrated using dynamic rheological measurements. These types of supramolecular PFPEs are anticipated to be useful for a number of emerging areas in lubrication. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3598–3606

We present the effect of molecular weight (MW) of polyelectrolytes (PEs) on the disintegration behavior of weak PE multilayer films consisting of linear poly(ethylene imine) (LPEI) and poly(methacrylic acid) (PMAA). The multilayer films prepared by the spin-assisted layer-by-layer deposition have well-ordered internal structures and also show the linear thickness growth behavior regardless of MWs of PMAA. The well-defined weak PE multilayer films were subject to disintegration into bulk solution when the electrostatic interactions between LPEI and PMAA layers were reduced by treatment at pH 2. However, we demonstrated the change in the disintegration mode and kinetics (i.e., from burst erosion to controlled surface erosion) as a function of MW of PMAA based on neutron reflectivity and quartz crystal microbalance with dissipation, revealing the correlation between the structural changes and the viscoelastic responses of the weak PE films upon pH treatment. Also, the unique swelling behavior as well as the ...

3D TiO2 photoanodes in dye-sensitized solar cells (DSCs) are fabricated by the soft lithographic technique for efficient light trapping. An extended strategy to the construction of randomized pyramid structure is developed by the conventional wet-etching of a silicon wafer for low-cost fabrication. Moreover, the futher enhancement of light absorption resulting in photocurrent increase is achieved by combining the 3D photoanode with a conventional scattering layer.

An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li–S batteries, exhibiting high specific capacity (823 mA h g−1 at 100 cycles) and enhanced capacity retention. A polymerization method for converting elemental sulfur into a chemically stable, processable and electrochemically active copolymer has been described. This methodology — termed inverse vulcanization — is conducted by a one-step process using liquid sulfur, as both reaction medium and reactant, and vinylic comonomers to form polymeric materials with a high content of sulfur (50–90 wt%).

Transparent, thermally insulating, and UV-blocking organosilicate (OS) hybrid films were successfully demonstrated based on nano-sized silica/titania hybrid hollow shells (STHs). A large scale of STHs were conveniently prepared by using nano-sized poly(acrylic acid) (PAA) colloidal aggregates as templates, tetraethyl orthosilicate (TEOS) as a silica precursor, and titanium tetrabutoxide (TBOT) as a titania presursor by the simple sol-gel reaction. The prepared STHs showed the strong affinity with OS matrices and the excellent transparency within the OS matrices due to their small size about 50 nm. Furthermore, TiO2 shells formed on the SiO2 shell surfaces selectively absorbed the UV light maintaining high transparency of the OS hybrid films in the visible range. The hollow inner space within the STHs enables the interruption of heat flow and the reduction in thermal diffusivity of the OS hybrid films, showing that the thermal conductivity of the OS hybrid films decreased about 20% when compared with the OS films without STHs. With these advantages, multifunctional OS hybrid films with thermally insulating and UV-blocking properties as well as excellent transparency in the visible range could be achieved. Open image in new window

Current trends in technology development demand increased miniaturization and higher level integration of electronic and photonic components. Such needs arise in emerging imaging systems, optoelectronic devices, optical interconnects and photonic integrated circuits. Compact, integrated photonics requires high refractive index materials, which primarily comprise crystalline and amorphous semiconductors, as well as chalcogenide glasses, which can possess refractive indices higher than 4 and good infrared transparency. There is currently no high refractive index (n ~ 2 or above) that has the low cost production and ease of processing available in optical polymers. Such polymers would potentially cover applications that are not convenient or possible with crystalline and vitreous semiconductors. Examples of such applications include micro lens arrays for image sensors, optical adhesives for bonding and antireflection coatings, and high contrast optical waveguides. While much of the focus has been in the telecommunications transparency regions, significant new opportunities exist for a polymer which is capable of transmitting efficiently in the MWIR region. While there are polymers that have been synthesized with refractive indices as high as 1.75, these polymers are generally conjugated and incorporate heteroatoms such as sulfur or metals, and generally have complex and expensive syntheses. Here we report on new chalcogenide based copolymers with very high refractive index (n ~ 2) that also have good optical transmission properties in the near-, short- and mid-wave infrared up to 5µm. These polymers are rich in sulfur, have low hydrogen content and were made using inverse vulcanization.

Thick inorganic shells endow colloidal nanocrystals (NCs) with enhanced photochemical stability and suppression of photoluminescence intermittency (also known as blinking). However, the progress of using thick-shell heterostructure NCs in applications has been limited due to the low photoluminescence quantum yield (PL QY ≤ 60%) at room temperature. Here, we demonstrate thick-shell NCs with CdS/CdSe/CdS seed/spherical quantum well/shell (SQW) geometry that exhibit near-unity PL QY at room temperature and suppression of blinking. In SQW NCs, the lattice mismatch is diminished between the emissive CdSe layer and the surrounding CdS layers as a result of coherent strain, which suppresses the formation of misfit defects and consequently permits ∼100% PL QY for SQW NCs with a thick CdS shell (≥5 nm). High PL QY of thick-shell SQW NCs is preserved even in concentrated dispersion and in film under thermal stress, which makes them promising candidates for applications in solid-state lightings and luminescent solar concentrators.