Matched‐dual‐polymer electrochromic lenses,using new cathodically coloring conducting polymers,with exceptional performance and incorporated into automated sunglasses

Reported are syntheses of several new monomer precursors of cathodically coloring conducting polymers (CPs), based on a propylene dioxythiophene skeleton. These are shown to yield CPs—both as homopolymers and as copolymers—that are nearly “perfectly” matched electrochemically and electrochromically with a set of anodically coloring poly(aromatic amines), for use in dual‐polymer electrochromic lenses. Resulting dual‐polymer electrochromic lenses display very high light/dark contrast (typically up to 70/7% or 50/0.5% Transmission (integrated over visible spectrum, vs. air reference), Haze < 2%, very high cyclability (> 10 K cycles), multiyear shelf life, appealing transparent to dark‐blue‐black transition, and excellent optical memory. Dramatic lowering of switching time, from 8 to < 1 s, is demonstrated using unique applied‐potential algorithm resident on inexpensive Microcontroller chip. Working, practical dual‐polymer electrochromic spectacles are demonstrated with electrochromic lenses retrofitted to spectacles meeting ANSI Z87.1, GL‐PD 10–12 (U.S. military) specifications. These incorporate photosensor, rechargeable Li battery, Microcontroller, allow for automated operation. Ab‐initio‐design spectacles, also conforming to above specifications, are also demonstrated, with components seamlessly hidden within frame. To the best of our knowledge, the electrochromic lenses and sunglasses reported herein represent the best visible‐region electrochromic performance for dual‐polymer CP electrochromic systems to date and the first practical implementation in working sunglasses. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41043.     

Improved infrared spectroscopic method for the analysis of degree of N-deacetylation of chitosan

Various infrared spectroscopic techniques for the analysis of degree of N-deacetylation of chitosan were evaluated for accuracy. A new method was proposed which involved development of a calibration curve using the absorbance intensities of the chitosan infrared spectrum at 1655 and 3450 cm⁻¹. The degree of N-deacetylation of various chitosan samples was then determined by using the absorption ratios [A₁₆₅₅/A₃₄₅₀] in the equation of the calibration curve. This method yielded results which were superior to those of any of the previously reported infrared spectroscopic methods tested herein. Received: 27 March 1997/Revised: 16 May 1997/Accepted: 22 May 1997     

Reduction in percolation threshold of injection molded high‐density polyethylene/exfoliated graphene nanoplatelets composites by solid state ball milling and solid state shear pulverization

Previous work showed that high density polyethylene (HDPE)/exfoliated graphene nanoplatelets (GNP) nanocomposites fabricated with melt extrusion followed by injection molding had a relatively high percolation threshold of between 10 and 15 vol % GNP loading. To lower the percolation threshold of injection molded HDPE/GNP nanocomposites, two special processing methods were investigated: solid state ball milling (SSBM) and solid state shear pulverization (SSSP). Results have confirmed that the percolation threshold of HDPE/GNP nanocomposites could be reduced to between 3 and 5 vol % GNP loading by these two approaches. The mechanism by which SSBM and SSSP are capable of producing lower percolation is to coat the polymer surface with GNP platelets which facilitates the formation of conductive networks during injection molding. However, it was found that HDPE/GNP nanocomposites obtained from these two techniques exhibited lower mechanical properties at high GNP loadings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Behavior of Pt Atoms on Oxide Supports During Reduction Treatments at Elevated Temperatures,Characterized by Aberration Corrected Stem Imaging

Abstract  

Aberration-corrected scanning transmission electron microscopy at the sub-?ngstr?m resolution allows imaging the structure of catalytic materials at the single atom level and permits fundamental studies of the behavior of heavy metal catalytic species as a result of elevated temperature gas-treatments. The present study is aimed at understanding the development of clusters and nanoparticles of Pt on γ-alumina during reduction treatments of a pre-oxidized highly dispersed catalyst. A special built ex situ reactor and a specimen holder allowing cyclic anaerobic transfer between the reactor and microscope were used for the study. The number of atoms in a nascent cluster can be determined along with the general shape of the cluster. Reduction experiments without air exposure of the sample showed that although clusters are formed at 500 °C, many Pt atoms are not associated with the cluster and are still dispersed on the catalyst support. After a 700 °C reduction, all of the Pt atoms are associated with the clusters. Movement of the clusters on the catalyst support is different depending upon the catalyst support.     

Impact of nanotube density and alignment on the elastic modulus near the top and base surfaces of aligned multi-walled carbon nanotube films

The mechanical compliance of vertically aligned carbon nanotube (VACNT) films renders them promising as interface materials that can accommodate thermal expansion mismatch. Here we study the relationship between the detailed morphology and elastic modulus of multi-walled VACNT films with thicknesses ranging from 98 to 1300 μm. A systematic analysis of scanning electron micrographs reveals variations in nanotube alignment and density among samples and within different regions of a given film. Nanoindentation of both top and bottom film surfaces using an atomic force microscope with spherical indenters with radii between 15 and 25 μm provides evidence of the modulus differences. The top surface is shown to have a higher modulus than the base, with out-of-plane modulus values of 1.0–2.8 MPa (top) and 0.2–1.4 MPa (base). The indentation data and microstructural information obtained from electron microscopy are interpreted together using an open cell foam model to account for differences in nanotube alignment and density, which are generally lower at the base and yield predictions that are consistent with the modulus data trends. This work shows that microstructure analysis complements property measurements to improve our understanding of nanostructured materials.     

Electrical conductivity of polymer blends of poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate): N-methyl-2-pyrrolidinone and polyvinyl alcohol

The goal of this study is to determine the electrically conductivity of the polymers poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate): N-methyl-2-pyrrolidinone (PEDOT: PSS: NMP) and PEDOT: PSS when blended with polyvinyl alcohol (PVA). While the conducting polymers have high conductivity when not blended with PVA, they are brittle and difficult to spin-coat. Thus, the motivation for this study is to develop blends of these two conducting polymers with PVA to produce a material with optimized mechanical properties and that can also be spin-coated. The blends are produced using aqueous preparations of these materials. Mixtures of various weight percentages (wt %) of PEDOT: PSS: NMP and PEDOT: PSS are prepared and spin-coated on glass slides to form thin films. In the blends, the film conductivity increases with increasing content of either PEDOT: PSS: NMP or PEDOT: PSS. For example, 100 wt % of PEDOT: PSS: NMP and 60 wt % of PEDOT: PSS: NMP blended with PVA exhibit conductivities of, respectively, 10 and 4.02 S/cm. In contrast, conductivities of only 0.0525 and 0.000506 S/cm are observed, respectively, for 100 wt % of PEDOT: PSS and 60 wt % of PEDOT: PSS content in the PEDOT: PSS/PVA blends (No NMP). The addition of the NMP enhances the electrical conductivity by two to five orders of magnitude (depending on the amount of PVA in the blend) due to conformational change of PEDOT chains. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Product design: Formulation of a screen-printable sintering-type conductive paste

Due to the complexity of the screen-printing operation and the rheological behaviors of the screen-printable paste, such a paste is usually formulated by trial-and-error. In this report, a systematic procedure, based on heuristics and mechanistic models, for the design of a screen-printable paste is developed. The procedure is demonstrated by a case study of the formulation of a conductive paste of copper particles.     

An adaptable luminescence resonance energy transfer assay for measuring and screening protein-protein interactions and their inhibition

Protein-protein interactions (PPIs) are central to biological processes and represent an important class of therapeutic targets. Here we show that the interaction between FK506-binding protein 12 fused to green fluorescent protein (GFP-FKBP) and the rapamycin-binding domain of mTor fused to Escherichia coli dihydrofolate reductase (FRB-eDHFR) can be sensitively detected (signal-to-background ratio (S/B)>100) and accurately quantified within an impure cell lysate matrix using a luminescence resonance energy transfer (LRET) assay. Ascomycin-mediated inhibition of GFP-FKBP-rapamycin-FRB-eDHFR complex formation was also detected at high S/B ratio (>80) and Z'-factor (0.89). The method leverages the selective, stable binding of trimethoprim (TMP)-terbium complex conjugates to eDHFR, and time-resolved, background-free detection of the long-lifetime (～ms) terbium-to-GFP LRET signal that indicates target binding. TMP-eDHFR labeling can be adapted to develop high-throughput screening assays and complementary, quantitative counter-screens for a wide variety of PPI targets with a broad range of affinities that may not be amenable to purification.     

Response to walnut olfactory and visual cues by the parasitic wasp Diachasmimorpha juglandis

Diachasmimorpha juglandis is a specialist parasitoid attacking fly larvae in the genus Rhagoletis that feed exclusively on walnut fruit husks. In a free-foraging assay comparing response to uninfested, infested, and mechanically damaged fruits, we first determined that D. juglandis use host feeding damage on the fruit as a cue for host presence. In another free-foraging assay that used artificial walnut models and wind tunnel experiments, D. juglandis distinguished infested from uninfested fruits by using either olfactory or visual cues separately. However, the response rate of wasps in the wind tunnel was raised considerably when visual cues were also available. We analyzed the volatile compounds emitted by cohorts of uninfested, mechanically damaged, and infested fruits 1, 3, 5, 8, and 10 days after oviposition by flies into the infested fruits. Total volatile emissions did not differ significantly among treatments, but quantitative changes in volatiles distinguished infested fruits from uninfested and damaged fruits. The fact that parasitoids did not distinguish between infested and damaged fruits in assays where damage was visible indicates that they rely on visual cues when those are available.     

Combustion characteristics of candles made from hydrogenated soybean oil

Hydrogenated soybean oil, referred to as soywax by candle makers, is a renewable and biodegradable alternative to paraffin wax in candle manufacturing. Soywax was investigated for its tendency to produce soot as well as potentially harmful organic volatiles (acrolein, formaldehyde, and acetaldehyde) during combustion. Beeswax and paraffin candles were used as references. A considerable amount of soot was produced from the combustion of paraffin candles, but little or none was observed from soywax candles. Compared to paraffin candles, soywax candles burned at a significantly slower rate and required less air. Small amounts of formaldehyde were detected and quantified in the fumes of burning paraffin candles. However, formaldehyde, peaks found in the chromatograms of soy- and beeswax candles were similar to or slightly higher than that of the blank. Since soywax candles exhibited burning properties similar to those of beeswax candles, soywax shows promise in candle applications.