Star-shaped alkylated poly(glycerol methacrylate) reverse micelles: Synthesis and evaluation of their solubilizing properties in dichloromethane

Amphiphilic star-shaped polymers were synthesized by atom transfer radical polymerization (ATRP). Four-, 5-, and 6-arm ATRP initiators were prepared and used to polymerize glycidylmethacrylate. The resulting polymers were hydrolyzed to yield poly(glycerolmethacrylate)s (PG_OHMAs), and then partially esterified with lauroyl or stearoyl chloride (40–60 mol % vs. hydroxyl groups). Alkylated PG_OHMAs were found to assemble into 20–60 nm aggregates in dichloromethane (DCM) above a critical concentration. Particle size essentially depended on the branching degree of the polymer. The micelles were extremely efficient in extracting Congo red from water into DCM, with the highest incorporations (97 mg/g) obtained for the 6-arm polymer modified with stearoyl chloride (60 mol %). The entrapment efficiency for the latter was further improved in alkaline solution. The high level of incorporation achieved for these amphiphilic multiarm polymers suggests that such reverse micelles could be potentially useful as drug delivery systems and nanoreactors in catalytic organic reactions or for water purification. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2425–2435, 2007     

Modification of Rhodium Catalyst with Stibines for Hydroformylation of 1‐Pentene

Homogeneous hydroformylation of 1‐pentene under synthesis gas experimental conditions was studied using RhClCO(PPh₃)₂ complex with different triarylstibines. Three different stibine ligands SbR₃ [where R = 2,4,6‐mesityl (TMS), 2‐furyl (TFS), 2‐N,N‐dimethylbenzylamine (TDMBAS)], have been tested. It is interesting to note that 2:1 addition of these stibine ligands to the RhClCO(PPh₃)₂ complex catalyst increases the aldehydes yields with an appreciable n:iso ratio. The catalytic activity of the system shows a TDMBAS > TMS > TFS pattern which indicates that not only basicity of the ligand alone is playing a role in the activity but the steric effect is also very important, and it is combination of these two factors that contributes to the resulting catalytical activity. The maximum yield of aldehydes obtained were 98.7% with n/iso = 1.4 when RhClCO(PPh₃)₂ + TFS system was used and 93.7% with n/iso = 2.43 when TDMBAS ligand was studied.     

On polyhedra induced by point sets in space

Given a set S of n?3 points in the plane (not all on a line) it is well known that it is always possible to polygonize S, i.e., construct a simple polygon P such that the vertices of P are precisely the given points in S. For example, the shortest circuit through S is a simple polygon. In 1994, Grünbaum showed that an analogous theorem holds in R³. More precisely, if S is a set of n?4 points in R³ (not all of which are coplanar) then it is always possible to polyhedronize S, i.e., construct a simple (sphere-like) polyhedron P such that the vertices of P are precisely the given points in S. Grünbaum's constructive proof may yield Schönhardt polyhedra that cannot be triangulated. In this paper several alternative algorithms are proposed for constructing such polyhedra induced by a set of points, which may always be triangulated, and which enjoy several other useful properties as well. Such properties include polyhedra that are star-shaped, have Hamiltonian skeletons, and admit efficient point-location queries. We show that polyhedronizations with a variety of such useful properties can be computed efficiently in O(nlogn) time. Furthermore, we show that a tetrahedralized, xy-monotonic, polyhedronization of S may be computed in time O(n^1+ε), for any ε>0.     

Effect of non-zero Schottky barrier on the J-V characteristics of organic diodes

Current-voltage (J -Vcharacteristics of poly(3-hexylthiophene) (P3HT) are studied at different temperatures upto high voltages ∼ 20 V in the hole-only device configuration. The characteristics are studied in the temperature range 310-210K. In the intermediate voltage range the J -V characteristics follow J V ^l+1 , where l > 1 . As the voltage increases to high values J still varies as a power law i.e. as V^m, but contrary to the literature result m becomes < 2 . This behavior is explained theoretically in terms of non-zero injection Schottky barriers. The complete analytical expressions for the actual trap filled limit voltage (V′ _TFL) and J -V curves beyond V′ _TFL are presented.     

Structural stability and electronic properties of GaSb nanowires

The structural stability and electronic properties of four different shapes of GaSb nanowire have been studied by ab-initio method using the generalized gradient approximations. The different structures were two atom linear wire, two atom zigzag wire, four atom square wire and six atom hexagonal wire. The geometry optimization and the stability of all nanowires were investigated. We explore the minimum energy atomic configuration for all the considered shapes. We find that four atom square wire configuration has greater stability in comparison to other shapes. The analysis of density of states and band structures of optimized nanowires predicts that semiconducting nanowires may be metallic or semiconducting. The behavior entirely depends upon the geometrical structure.     

Rhodium(I) carbonyl complexes of triphenylphosphine chalcogenides and their catalytic activity

Rhodium(I) carbonyl complexes [Rh(CO)₂ClL] where L = Ph₃PO, Ph₃PS and Ph₃PSe, were synthesized and characterized by elemental analysis, i.r. and by ¹H-, ¹³C- and ³¹P-n.m.r. spectroscopy. The vBD;(CO) band frequencies in the complexes follow the order: Ph₃PO > Ph₃PS > Ph₃PSe, in keeping with the hard/soft nature of the interactions. The complexes undergo oxidative additions with electrophiles such as MeI, PhCH₂Cl and I₂ to give, e.g. [Rh(CO)(COMe)ClIL] which react with PPh₃ to give trans-[Rh(CO)Cl(PPh₃)₂]. The catalytic activity of the [Rh(CO)₂ClL] complexes in carbonylation of MeOH is higher than that of the well-known [Rh(CO)₂I₂]⁻ species. This revised version was published online in June 2006 with corrections to the Cover Date.     

Room-temperature biosynthesis of ferroelectric barium titanate nanoparticles

The syntheses of inorganic materials by biological systems is characterized by processes that occur close to ambient temperatures, pressures, and neutral pH, as is exemplified by biosilicification and biomineralization processes in nature. Conversely, laboratory-based syntheses of oxide materials often require extremes of temperature and pressure. We have shown here the extracellular, room-temperature biosynthesis of 4-5 nm ternary oxide nanoparticles such as barium titanate (BT) using a fungus-mediated approach. The tetragonality as well as a lowered Curie transition temperature in sub-10 nm particles was established, and the ferroelectricity in these particles was shown using Kelvin probe microscopy.     

Fabrication and electrochemical performance of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> impregnated porous YSZ cathode

La_0.5Sr_0.5CoO₃-yttria-stabilized zirconia (LSCO-YSZ) composite cathode for solid oxide fuel cell (SOFC) has been fabricated by wet impregnation method. Nitrate precursors of La, Sr, and Co have been impregnated into the pre-sintered porous YSZ matrix, which is converted into LSCO phase after calcination at 850 °C in the presence of glycine as confirmed from X-ray diffraction. LSCO of 5, 7, and 10 wt% impregnated porous YSZ have been electrochemically characterized using 2-probe AC conductivity method. Maximum ionic conductivity of 0.27 S/cm at 800 °C and activation energy of 0.15 eV between 600 and 800 °C have been observed for 10 wt% LSCO-YSZ cathode. Area-specific resistance of 1.01 Ω cm² at 800 °C is estimated for the electrolyte-supported half-cell (10 wt% LSCO-YSZ/YSZ). After testing the LSCO-YSZ cathode matrix, the electrolyte-supported full cell (10 wt% LSCO-YSZ/YSZ/NiO-YSZ) has been tested and produced maximum power density 51.12 mW/cm² (109.38 mA/cm²) at 800 °C. The electrolyte-supported full cell exhibited 6 Ω cm² electrode polarization at 800 °C in H₂, which is in higher side leading to low performance. LSCO-YSZ/YSZ/NiO-YSZ SOFC found to give stable performance up to 2 h and scanning electron microscopy analysis has been carried out before and after cell testing to assess the morphological changes.     

Transport in Porous Media

Table of Contents

Transport in Porous Media     

Interaction between phospholipid vesicular structures with long chain zwitterionic surfactants

Solubilization of different zwitterionic phospholipid vesicles structures such as L--phosphatidylcholine (PC) and 1,2-didecanoyl-sn-glycero-3-phosphocholine (DPC) have been studied in aqueous bulk by using zwitterionic surfactant dimethylhexadecylammoniopropanesulfonate (HPS). This has been done by studying the aggregation of HPS in pure water and in the presence of 7–36 M of fixed concentrations of each lipid with the help of pyrene fluorescence intensity (I ₁/I ₃) measurements. The fluorescence measurements showed that HPS monomers undergo two kinds of aggregation process, which were identified by the three breaks in a plot of pyrene fluorescence versus HPS concentration. The first two breaks, C ₁ and C ₂, indicate the onset and completion of vesicle solubilization respectively, upon incorporation of HPS monomers into the vesicles and led to solubilization in the form of mixed micelles. This process was not clearly visible at low lipid concentration. We evaluated the partition coefficient (K), which defines the degree of partitioning of surfactant monomers into the vesicles with respect to the aqueous medium. A high K value of HPS-lipid aggregates indicates the stronger interactions between surfactant and lipid vesicles. The K values evaluated for PC and DPC are quite close to each other, which indicates that K values were independent of phospholipid chain length.