Periodically Grafted Amphiphilic Copolymers: Effects of Steric Crowding and Reversal of Amphiphilicity

Two series of periodically clickable polyesters were prepared; one of them carries alkylene segments along its backbone, whereas the other carries poly(ethylene glycol) (PEG) segments. These polyesters were clicked with either MPEG-350 azide or docosyl (C22) azide to yield periodically grafted amphiphilic copolymers (PGACs) carrying either flexible hydrophilic or crystallizable hydrophobic backbone segments. The immiscibility between hydrocarbon and PEG segments causes both of these systems to fold in either a zigzag or hairpin-like conformation; the hairpin-like conformation appears to be preferred when flexible PEG segments are present in the backbone. The folded chains further reorganize in the solid state to develop a lamellar morphology that permits the collocation of the PEG and hydrocarbon (HC) segments within alternate domains; evidence for the self-segregation was gained from DSC, SAXS, and AFM studies. SAXS studies revealed the formation of an extended lamellar structure, whereas AFM images showed uniform layered morphology with layer heights that matched reasonably well with the interlamellar spacing obtained from the SAXS study. Labeling One representative PGAC, carrying crystallizable long alkylene segments in the backbone and pendant PEG-350 side chains, with a small mole fraction of pyrene fluorophore permitted the examination of the conformational transition that occurs upon going from a good to a poor solvent; this single-chain folded conformation, we postulate, is the intermediate that organizes into the lamellar morphology.

Robust, metallic Pd17Se15 and Pd7Se4 phases from a single source precursor and their use as counter electrodes in dye sensitized solar cells

Thin films of conducting palladium selenide phases (Pd17Se15 and Pd7Se4) are prepared using a single source molecular precursor by thermolysis. Varying the mole ratios of palladium and selenium precursors results in palladium organo-selenolate complexes which on thermolysis at different temperatures yield Pd17Se15 and Pd7Se4 phases that are very stable and adherent to the substrate. The organo-selenolate complexes are characterized using small angle XRD, Se-77 NMR and thermogravimetric analysis (TGA). The palladium selenide films are characterized by various techniques such as XRD, XPS, TEM and SEM. Electrical conductivities of the films are determined using the four probe method. The strong adherence of the films to glass substrates coupled with high corrosion resistant behavior towards strong acid and alkaline environments render them to be very effective as electrocatalysts. The catalytic activity towards the I-3(-)/I- redox couple, which is an important reaction in the regeneration of the dye in a dye-sensitized solar cell, is studied. Between the two phases, the Pd17Se15 film shows superior activity as the counter electrode for dye sensitized solar cells with a photocurrent conversion efficiency of 7.45%.

Solubilities of 10-undecenoic acid and geraniol in supercritical carbon dioxide

The solubilities of 10-undecenoic acid and geraniol in supercritical carbon dioxide were measured at 308, 313,323 and 333K, and at pressures of 10-18 MPa. Solubilities (in mole fraction),ranged from 0.4 x 10(-3) to 17.4 x 10(-3) for 10-undecenoic acid and 2.7 x 10(-3) to 25 x 10(-3) for geraniol, respectively. The AARD was around 11% and 5% for these models for 10-undecenoic acid and geraniol, respectively. The solubilities of both compounds showed retrograde behavior wherein the solubilities decrease with temperature at isobaric conditions. The solubility of geraniol was higher than 10-undecenoic acid at all investigated temperatures and pressures. The data were found to be self consistent based on the Mendez-Santiago model. New models based on association theory using van Laar and Margules activity coefficient models for solute in liquid phase were derived, and used to correlate the solubilities. (C) 2015 Elsevier B.V. All rights reserved.

Electron mobility in few-layer MoxW1-xS2

Heterostructures of two-dimensional (2D) layered materials are increasingly being explored for electronics in order to potentially extend conventional transistor scaling and to exploit new device designs and architectures. Alloys form a key underpinning of any heterostructure device technology and therefore an understanding of their electronic properties is essential. In this paper, we study the intrinsic electron mobility in few-layer MoxW1-xS2 as limited by various scattering mechanisms. The room temperature, energy-dependent scattering times corresponding to polar longitudinal optical (LO) phonon, alloy and background impurity scattering mechanisms are estimated based on the Born approximation to Fermi's golden rule. The contribution of individual scattering rates is analyzed as a function of 2D electron density as well as of alloy composition in MoxW1-xS2. While impurity scattering limits the mobility for low carrier densities (<2-4x10(12) cm(-2)), LO polar phonon scattering is the dominant mechanism for high electron densities. Alloy scattering is found to play a non-negligible role for 0.5 < x < 0.7 in MoxW1-xS2. The LO phonon-limited and impurity-limited mobilities show opposing trends with respect to alloy mole fractions. The understanding of electron mobility in MoxW1-xS2 presented here is expected to enable the design and realization of heterostructures and devices based on alloys of MoS2 andWS(2).

Experimental solubilities of two lipid derivatives in supercritical carbon dioxide and new correlations based on activity coefficient models

The solubilities of two lipid derivatives, geranyl butyrate and 10-undecen-1-ol, in SCCO2 (supercritical carbon dioxide) were measured at different operating conditions of temperature (308.15 to 333.15 K) and pressure (10 to 18 MPa). The solubilities (in mole fraction) ranged from 2.1 x 10(-3) to 23.2 x 10(-3) for geranyl butyrate and 2.2 x 10(-3) to 25.0 x 10(-3) for 10-undecen-1-ol, respectively. The solubility data showed a retrograde behavior in the pressure and temperature range investigated. Various combinations of association and solution theory along with different activity coefficient models were developed. The experimental data for the solubilities of 21 liquid solutes along with geranyl butyrate and 10-undecen-1-ol were correlated using both the newly derived models and the existing models. The average deviation of the correlation of the new models was below 15%.

Electron mobility in few-layer MoxW1-xS2

Heterostructures of two-dimensional (2D) layered materials are increasingly being explored for electronics in order to potentially extend conventional transistor scaling and to exploit new device designs and architectures. Alloys form a key underpinning of any heterostructure device technology and therefore an understanding of their electronic properties is essential. In this paper, we study the intrinsic electron mobility in few-layer MoxW1-xS2 as limited by various scattering mechanisms. The room temperature, energy-dependent scattering times corresponding to polar longitudinal optical (LO) phonon, alloy and background impurity scattering mechanisms are estimated based on the Born approximation to Fermi's golden rule. The contribution of individual scattering rates is analyzed as a function of 2D electron density as well as of alloy composition in MoxW1-xS2. While impurity scattering limits the mobility for low carrier densities (<2-4x10(12) cm(-2)), LO polar phonon scattering is the dominant mechanism for high electron densities. Alloy scattering is found to play a non-negligible role for 0.5 < x < 0.7 in MoxW1-xS2. The LO phonon-limited and impurity-limited mobilities show opposing trends with respect to alloy mole fractions. The understanding of electron mobility in MoxW1-xS2 presented here is expected to enable the design and realization of heterostructures and devices based on alloys of MoS2 andWS(2).