Rapid fabrication of organic/organic photonic bandgap films with tuneable mechanical properties using blended polymer spheres

In this study, the photonic bandgap (PBG) film with tunable mechanical properties and photonic stop band was prepared by a simple and feasible approach. Colloid polymer spheres with a relatively large diameter (approximate D_n of 200 nm) and different glass transition temperatures (T_g) were blended with small polystyrene (PS) latex (D_n = 20 nm) and were subsequently casted on a substrate for 3 h at 50°C for self‐assembly of the PBG film. The monodispersed polymer spheres were synthesized by soap‐free emulsion polymerization in the boiling state. The T_g values of the spheres were predetermined based on the Fox equation, and designed to fall in the region of ?34°C to 112°C. Small PS could also be synthesized by this approach using the comonomer, sodium p‐styrenesulfonate (NaSS), to ensure the small diameter. The long‐range ordered structure constructed by embedding the small PS in the PBG film was indirectly confirmed on the basis of SEM analysis, from which the monochromatic film color was determined based on Bragg's diffraction law. Tunable film color was achieved by adjusting the diameter of the spheres, as evaluated using UV–Vis. Tunable mechanical properties of the PBG film were also achieved by varying the T_g of the spheres or the filling ratio of small PS. Based on these approaches, the ultimate tensile strength could be tuned in the region between 0.39 to 4.7 Mpa, and the relative strain could be varied from 1236% to 16%, illustrative of the excellent deformability of the film. Furthermore, by variation of these two parameters, the film properties could be changed from typical elastomer behavior to brittle plastic polymer type behavior, greatly extending the prospective application fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40276.     

Rheological behavior of cellulose nanocrystal suspension: Influence of concentration and aspect ratio

The steady and dynamic rheological behaviors of two cellulose nanocrystal (CNC) suspensions were investigated over a wide range of concentrations. The viscosity, storage and loss modules increased with increasing CNC concentration, and both CNC suspensions showed three regions in a viscosity‐concentration graph. The two critical concentrations depended on the aspect ratio and corresponded to the overlap and gelation concentration. Because of the higher aspect ratio, switchgrass CNC suspension transitioned into a biphasic state and formed a hydrogel at lower concentrations than those of cotton CNC suspensions. Furthermore, the complex viscosities of both CNC suspensions were higher than their steady viscosities; therefore, neither CNC suspension followed the Cox–Merz rule, which may be attributed to the existence of a liquid crystal domain in each suspension. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40525.     

Viscoelastic and rheological behavior of concentrated colloidal suspensions

Molecular approaches are discussed to the density (), viscoeleastic (), and rheological () behavior of the viscosity(,,) of concentrated colloidal suspensions with 0.3 < < 0.6, where, is the volume fraction, the applied frequency, and ; the shear rate. These theories are based on the calculation of the pair distribution functionP ₂(r,,), wherer is the relative position of a pair of colloidal particles. The linear viscoelastic behavior(,,=0) follows from an equation forP ₂(r,,) derived from the Smoluchowski equation for small, generalized to large by introducing the spatial ordering and (cage) diffusion typical for concentrated suspensions. The rheological behavior(,,=0) follows from an equation forP ₂(r,) of a dense hard-sphere fluid derived from the Liouville equation. This leads to a hard-sphere viscosity^hs(,) which yields the colloidal one(,) by the scaling relation(,) ₀=^hs(,) _B, where ₀ is the solvent viscosity. _B is the dilute hard-sphere (Boltzmann ) viscosity and the's are appropriately scaled,(,) and(,) agree well with experiment. A unified theore for(,,) is clearly needed and pursued.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994. Boulder, Colorado, U.S.A.     

Light‐Activated,Multi‐Semiconductor Hybrid Microswimmers

Using a dynamic fabrication process, hybrid, photoactivated microswimmers made from two different semiconductors, titanium dioxide (TiO₂) and cuprous oxide (Cu₂O) are developed, where each material occupies a distinct portion of the multiconstituent particles. Structured light‐activated microswimmers made from only TiO₂ or Cu₂O are observed to be driven in hydrogen peroxide and water most vigorously under UV or blue light, respectively, whereas hybrid structures made from both of these materials exhibit wavelength‐dependent modes of motion due to the disparate responses of each photocatalyst. It is also found that the hybrid particles are activated in water alone, a behavior which is not observed in those made from a single semiconductor, and thus, the system may open up a new class of fuel‐free photoactive colloids that take advantage of semiconductor heterojunctions. The TiO₂/Cu₂O hybrid microswimmer presented here is but an example of a broader method for inducing different modes of motion in a single light‐activated particle, which is not limited to the specific geometries and materials presented in this study.     

Localized surface plasmon resonance enhanced photoluminescence of CdSe QDs in PMMA matrix on silver colloids with different shapes

Localized surface plasmon resonance (LSPR) enhanced photoluminescences (PL) from CdSe quantum dots (QDs) on worm-like or quasi-spherical silver colloids have been investigated. The shape of silver colloid film is controlled by annealing temperature (200 °C∼350 °C). Strong PL enhancements of CdSe QDs on both as-grown and annealed silver colloid films are observed. The results show that the PL enhancement factor of CdSe QDs on worm-like silver colloid film reaches as high as 15-fold. Moreover, the enhancement factor is 5 times larger than that obtained from the quasi-spherical silver colloids. The superiority of worm-like silver nanostructure on LSPR enhanced photoluminescence is attributed to its larger size, hot spots and multiple dipole resonance modes coupling, which are induced by aggregation effect.     

Amplification of Resonant Rayleigh Light Scattering Response Using Immunogold Colloids for Detection of Lysozyme

A strategy for attomolar‐level detection of small molecule‐size proteins is reported based on Rayleigh light scattering spectroscopy of individual nanoplasmonic aptasensors by exploiting the outstanding characteristics of gold colloids to amplify the nontransparent resonant signal at ultralow analyte concentrations. The fabrication method utilizes thiol‐mediated adsorption of a DNA aptamer on the immobilized Au nanoparticle surface, the interfacial binding characteristics of the aptamer with its target molecules, and the antibody–antigen interaction through plasmonic resonance coupling of the Au nanoparticles. Using lysozyme as a model analyte for disease detection, the detection limit of the aptasensor is ～7 × 10³ aM, corresponding to the LSPR λ_max shift of ～2.25 nm. Up to a 380% increase in the localized resonant λ_max shift is demonstrated upon antibody binding to the analyte compared to the primary response during signal amplification using immunogold colloids. This enhancement leads to a limit of detection of ～7 aM, which is an improvement of three orders of magnitude. The results demonstrate substantial promise for developing coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes.     

Colloid‐in‐Liquid Crystal Gels that Respond to Biomolecular Interactions

This paper advances the design of stimuli‐responsive materials based on colloidal particles dispersed in liquid crystals (LCs). Specifically, thin films of colloid‐in‐liquid crystal (CLC) gels undergo easily visualized ordering transitions in response to reversible and irreversible (enzymatic) biomolecular interactions occurring at the aqueous interfaces of the gels. In particular, LC ordering transitions can propagate across the entire thickness of the gels. However, confinement of the LC to small domains with lateral sizes of ～10 μm does change the nature of the anchoring transitions, as compared to films of pure LC, due to the effects of confinement on the elastic energy stored in the LC. The effects of confinement are also observed to cause the response of individual domains of the LC within the CLC gel to vary significantly from one to another, indicating that manipulation of LC domain size and shape can provide the basis of a general and facile method to tune the response of these LC‐based physical gels to interfacial phenomena. Overall, the results presented in this paper establish that CLC gels offer a promising approach to the preparation of self‐supporting, LC‐based stimuli‐responsive materials.     

Laser-Generated Supranano Liquid Metal as Efficient Electron Mediator in Hybrid Perovskite Solar Cells

Creating colloids of liquid metal with tailored dimensions has been of technical significance in nano-electronics while a challenge remains for generating supranano (<10 nm) liquid metal to unravel the mystery of their unconventional functionalities. Present study pioneers the technology of pulsed laser irradiation in liquid from a solid target to liquid, and yields liquid ternary nano-alloys that are laborious to obtain via wet-chemistry synthesis. Herein, the significant role of the supranano liquid metal on mediating the electrons at the grain boundaries of perovskite films, which are of significance to influence the carriers recombination and hysteresis in perovskite solar cells, is revealed. Such embedding of supranano liquid metal in perovskite films leads to a cesium-based ternary perovskite solar cell with stabilized power output of 21.32% at maximum power point tracing. This study can pave a new way of synthesizing multinary supranano alloys for advanced optoelectronic applications.