Molecular Heterojunctions of Oligo(phenylene ethynylene)s with Linear to Cruciform Framework

Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals. Dithiafulvene (DTF) is used as substituent group to the oligo(phenylene ethynylene) (OPE) molecular wires and different molecular structures based on OPE3 backbone (with linear to cruciform framework) are achieved, with viable molecular orbitals and HOMO–LUMO energy gaps. OPE3, OPE3–DTF, and OPE3–tetrathiafulvalene (TTF) can form good self‐assembled monolayers (SAMs) on Au substrates. Molecular heterojunctions based on these SAMs are investigated using conducting probe–atomic force microscopy with different tips (Ag, Au, and Pt) and Fermi levels. The calibrated conductance values follow the sequence OPE3–TTF > OPE3–DTF > OPE3 irrespective of the tip metal. Rectification properties (or diode behavior) are observed in case of the Ag tip for which the work function is furthest from the HOMO levels of the OPE3s. Quantum chemical calculations of the transmission qualitatively agree with the experimental data and reproduce the substituent effect of DTF. Zero‐bias conductance, and symmetric or asymmetric couplings to the electrodes are investigated. The results indicate that improved fidelity of molecular transport measurements may be achieved by systematic studies of homologues series of molecular wires applying several different metal electrodes.     

Landscapes of Challenge and Change: Contested Views of the Cairngorms National Park

The Scottish model of national parks reflects wider changes in the management of special or protected landscapes. This paper uses Ingold's dwelling conceptualisation of landscape to reflect on how material and cultural processes affect stakeholders' perceptions of the Cairngorms National Park in Scotland, UK. Important to understanding different views, is the separation, unique to the Cairngorms, of ‘the park’ from its management organisation. The paper argues that this separation creates a conceptual space for the negotiation of contested claims regarding the park. Such claims reflect not only the relationship between people and place, or as Ingold (2000) puts it, the landscape as it is known to those who dwell in it; they also represent vested interests and regimes of power concerning what happens in specific places. These claims do not reproduce simple splits between, for example, public/private or conservation/development but show a more complex picture.     

Constructing Homeownership Policy: Social Constructions and the Design of the Low-Income Homeownership Policy Objective

This paper offers a new perspective to explain how and why the U.S. federal government pursued a policy agenda that from the early-1990s promoted homeownership as the preferred housing tenure of choice for low-income households. Using policy design theory (Schneider &; Ingram 1997 Schneider, A. L. and Ingram, H. M. 1997. Policy Design for Democracy, Lawrence, KS: University Press of Kansas.  [Google Scholar]), this paper argues that the social constructions of homeownership, low-income households, and the private mortgage industry were instrumental in the development of policies to increase low-income homeownership. The benefits associated with homeownership, based on long-standing norms around success, stability, and the American Dream, justified government interventions to increase access to private mortgage markets for low-income households. This policy stance, however, did nothing to assist households with maintaining homeownership for the long term. The social constructions embedded in the rationales and implementation of these policies contributed to their failure to sustain homeownership and realize its benefits for low-income homeowners.     

Co‐optimization of SnS absorber and Zn(O,S) buffer materials for improved solar cells

Thin‐film solar cells consisting of earth‐abundant and non‐toxic materials were made from pulsed chemical vapor deposition (pulsed‐CVD) of SnS as the p‐type absorber layer and atomic layer deposition (ALD) of Zn(O,S) as the n‐type buffer layer. The effects of deposition temperature and annealing conditions of the SnS absorber layer were studied for solar cells with a structure of Mo/SnS/Zn(O,S)/ZnO/ITO. Solar cells were further optimized by varying the stoichiometry of Zn(O,S) and the annealing conditions of SnS. Post‐deposition annealing in pure hydrogen sulfide improved crystallinity and increased the carrier mobility by one order of magnitude, and a power conversion efficiency up to 2.9% was achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

Processing and thermal properties of composites based on recycled PET,sisal fibers,and renewable plasticizers

This investigation focuses on the preparation of bio‐based composites from recycled poly (ethylene terephthalate) (PET) and sisal fibers (3 cm, 15 wt %), via thermopressing process. Plasticizers derived from renewable raw materials are used, namely, glycerol, tributyl citrate (TBC) and castor oil (CO), to decrease the melting point of the recycled PET (T_m ∼ 265°C), which is sufficiently high to initiate the thermal decomposition of the lignocellulosic fiber. All used materials are characterized by thermogravimetric analysis and differential scanning calorimetry, and the composites are also characterized via dynamic mechanical thermal analysis. The storage modulus (30°C) and the tan δ peak values of CT [PET/sisal/TBC] indicate that TBC also acts as a compatibilizing agent at the interface fiber/PET, as well as a plasticizer. To compare different processing methods, rheometry/thermopressing and compression molding are used to prepare the recycled PET/sisal/glycerol/CO composites. These two different methods of processing show no significant influence on the thermal properties of these composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40386.     

Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.     

Comparison of two low-hazard organic solvents as individual and cosolvents for the fabrication of polysulfone membranes

Petroleum-derived solvents commonly used in membrane fabrication are often hazardous and toxic, so the investigation of safer alternatives is important. In this study, two low-hazard solvents, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate (Rhodiasolv® PolarClean) and gamma-valerolactone (GVL), were investigated as sole solvents and as cosolvents to cast polysulfone membranes via nonsolvent induced phase inversion. Normalized viscosity was introduced as an indicator of dope solution homogeneity and was used to compare the required time of mixing to achieve full dissolution of the polymer in the different solvents/solvent mixtures. All dope solutions made with low-hazard solvents were found to be more viscous than those made with traditional solvents, which meant additional mixing time was needed, and that fabricated membranes were morphologically different. With respect to operation, membranes cast from dope solutions containing equal amounts of PolarClean and GVL displayed the most similar flux curves and solute rejection to those made using the traditional solvent tested.     

Technical note: Use of an automated grooming brush by heifers and potential for radiofrequency identification-based measurements of this behavior

Healthy cattle readily use grooming brushes but this behavior subsides when animals become ill. Tracking use of a brush may provide an opportunity for health monitoring, especially if the process could be automated. We assessed how healthy heifers groom themselves on a brush and hypothesized that radiofrequency identification (RFID) could be used to accurately and automatically record this behavior. Angus and Hereford heifers (n = 16) were fitted with 2 ultra-high-frequency RFID ear tags and monitored in groups of 8 while housed in a pen with an electronic brush, video cameras, and 4 RFID antennas. Each heifer was observed for a 6-h period using continuous video recordings, and brush contact was characterized in terms of anatomic region involved (head/neck, trunk, or posterior) and when not touching the brush but within 1 body length of it. The RFID data were collected for the same period and then processed such that intervals of up to 16 s with no detections but contained between 2 recordings were also considered positive (animal in brush proximity). Brush proximity (RFID) was regressed against brush contact duration (video) and the sensitivity and specificity for each individual heifer calculated. Across heifers, the majority of brush use involved the head/neck, although a few heifers demonstrated relatively large amounts of posterior contact, which contributed to false-negative readings when antennas failed to read the ear tags. Furthermore, for the majority of time that animals were near the brush, they were not in contact with it but rather standing or lying nearby, resulting in false-positive readings. It follows that the ability of the RFID system to accurately detect brush contact varied widely across individual heifers (sensitivity 0.54–1.0; specificity 0.59–0.98), with RFID generally overestimating the duration of brush proximity relative to actual time spent in brush contact. The implication is that RFID-based ear tag recording of brush proximity relative to continuous video observations of contact does not yield accurate results in certain heifers and therefore, as currently configured, is not a reliable representation of this type of grooming behavior.     

Evaluation of an alkaline phosphatase-labeled oligonucleotide probe for the detection and enumeration of the thermostable-related hemolysin (trh) gene of Vibrio parahaemolyticus

Reliable methods are needed to detect total and pathogenic Vibrio parahaemolyticus. One marker of V. parahaemolyticus virulence is the thermostable-related hemolysin. We developed an alkaline phosphatase-labeled DNA probe method for the specific detection and enumeration of trh-positive V. parahaemolyticus by colony hybridization. The probe was tested against a panel of 200 bacterial strains and determined to be specific for trh-positive V. parahaemolyticus. Additionally, the trh alkaline phosphatase probe colony hybridization was successfully used to detect and enumerate trh-positive V. parahaemolyticus in seafood and water samples collected from the United States and the United Kingdom.