Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Oxidative Epigallocatechin Gallate Coating on Polymeric Substrates for Bone Tissue Regeneration

Plant derived flavonoids have not been well explored in tissue engineering applications due to difficulties in efficient formulations with biomaterials for controlled presentation. Here, the authors report that surface coating of epigallocatechin gallate (EGCG) on polymeric substrates including poly (L‐lactic acid) (PLLA) nanofibers can be performed via oxidative polymerization of EGCG in the presence of cations, enabling regulation of biological functions of multiple cell types implicated in bone regeneration. EGCG coating on the PLLA nanofiber promotes osteogenic differentiation of adipose‐derived stem cells (ADSCs) and is potent to suppress adipogenesis of ADSCs while significantly reduces osteoclastic maturation of murine macrophages. Moreover, EGCG coating serves as a protective layer for ADSCs against oxidative stress caused by hydrogen peroxide. Finally, the in vivo implantation of EGCG‐coated nanofibers into a mouse calvarial defect model significantly promotes the bone regeneration (61.52 ± 28.10%) as compared to defect (17.48 ± 11.07%). Collectively, the results suggest that EGCG coating is a simple bioinspired surface modification of polymeric biomaterials and importantly can thus serve as a promising interface for tuning activities of multiple cell types associated with bone fracture healing.     

Rapid DNA hybridization analysis using a PDMS microfluidic sensor and a molecular beacon.

A rapid DNA analysis has been developed based on a fluorescence intensity change of a molecular beacon in a PDMS microfluidic channel. Recently, we reported a new analytical method of DNA hybridization involving a PDMS microfluidic sensor using fluorescence energy transfer (FRET). However, there are some limitations in its application to real DNA samples because the target DNA must be labelled with a suitable fluorescent dye. To resolve this problem, we have developed a new DNA microfluidic sensor using a molecular beacon. By monitoring the change in the restored fluorescence intensity along the channel length, it is possible to rapidly detect any hybridization of the molecular beacon to the target DNA. In this case, the target DNA does not need to be labelled. Our experimental results demonstrate that this microfluidic sensor using a molecular beacon is a promising diagnostic tool for rapid DNA hybridization analysis.     

Composite Silica Particles Using a Mixture of Organosilane Monomers

Composite silica particles were synthesized by a two-step (acid-base) process in an aqueous solution with a mixture of organoalkoxysilane monomers. The two-step process separates the hydrolysis and condensation procedures to easily control condensation rate. In this study, the silane monomers used were phenyltrimethoxysilane (PTMS), vinyltrimethoxysilane (VTMS), methyltrimethoxysilane (MTMS), and tetraethyl-orthosilicate (TEOS). The physical properties of the resultant composite particles were investigated with the change in the molar ratio of monomers. The size of the particles increased with increasing the molar ratio of R_aSi(OR)₃/R_bSi(OR)₃ or R_aSi(OR)₃/TEOS (R_a: phenyl; R_b: vinyl, methyl).     

Synthesis and characterization of soluble polyimides containing trifluoromethyl groups in their backbone

A series of polyimides were synthesized from 2,2‐Bis(3,4‐dicarboxyphenyl)hexafluoropropane, 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane, and 4,4′‐oxydianiline by chemical imidization. The effects of the diamine ratios on the properties of the films were evaluated through the study of their thermal, electrical, and morphological properties. All the polymers exhibited better solubility in most of the organic solvents and hence were easily processable. Polyimides with more 2,2‐bis(3‐amino‐4‐hydroxyphenyl)‐hexafluoropropane exhibited better solubility and a low refractive index, which is highly desired for microelectronic applications. The dielectric constant and birefringence were strongly dependent on the fluorine content. With an increase in the fluorine substitution, both the dielectric constant and birefringence decreased. All the polymers exhibited high thermal stability (>400 °C). The absence of crystalline melting in differential scanning calorimetry and broad wide‐angle X‐ray diffraction patterns revealed the amorphous nature of the polymers, which was due to the presence of bulky CF₃ groups and hinged ether linkages of the diamine component. The residual stress values decreased with an increase in the 4,4′‐oxydianiline content, and the results were in agreement with the dielectric constant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4303–4312, 2004     

Thermal behavior of metallodendrimers possessing bis(terpyridinyl)Ru(II) connectivity and different surface functionality

A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru^(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004