Investigation of the quasi-ternary system LaMnO3-LaCoO3-“LaCuO3”—I: the series La(Mn0.5Co0.5)1−xCuxO3−δ

The La(Mn_0.5Co_0.5)_1−xCu_xO_3−δ series with x=0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8 and 1 was synthesized by the Pechini method to obtain insight into the phase formation in the quasi-ternary LaMnO₃-LaCoO₃-“LaCuO₃” system caused by the instability of LaCuO₃ under ambient conditions. After sintering at 1100°C some remarkable results were obtained: LaMn_0.3Co_0.3Cu_0.4O_3−δ crystallized as a single phase in the orthorhombic perovskite structure typical of LaCuO₃. Among the synthesized compositions this compound showed the highest electrical conductivity in air at 800°C (155 S cm⁻¹) and also the highest thermal expansion coefficient (α_30−800°C=15.4×10⁻⁶ K⁻¹). The LaCuO_3−δ composition also crystallized as a single phase but in a monoclinic structure although previous investigations have shown that other phases are preferably formed after sintering at 1100°C. The electrical conductivity and thermal expansion coefficient were the lowest within the series of compositions, i.e. 9.4 S cm⁻¹ and 11.9×10⁻⁶ K⁻¹, respectively.     

Insights into the retention mechanism of neutral organic compounds on polar chemically bonded stationary phases in reversed-phase liquid chromatography

The solvation parameter model is used to characterize the retention properties of a 3-aminopropylsiloxane-bonded (Alltima amino), three 3-cyanopropylsiloxane-bonded (Ultrasphere CN, Ultremex-CN and Zorbax SB-CN), a spacer bonded propanediol (LiChrospher DIOL) and a multifunctional macrocyclic glycopeptide (Chirobiotic T) silica-based stationary phases with mobile phases containing 10 and 20% (v/v) methanol-water. The low retention on the polar chemically bonded stationary phases compared with alkylsiloxane-bonded silica stationary phases arises from the higher cohesion of the polar chemically bonded phases and an unfavorable phase ratio. The solvated polar chemically bonded stationary phases are considerably more hydrogen-bond acidic and dipolar/polarizable than solvated alkylsiloxane-bonded silica stationary phases. Selectivity differences are not as great among the polar chemically bonded stationary phases as they are between the polar chemically bonded phases and alkylsiloxane-bonded silica stationary phases.     

Asymmetric Catalysis in Liquid Confinement: Probing the Performance of Novel Chiral Rhodium–Diene Complexes in Microemulsions and Conventional Solvents

The role of liquid confinement on the asymmetric Rh catalysis was studied using the 1,2-addition of phenylboroxine ( 2 ) to N-tosylimine 1 in the presence of [RhCl(C₂H₄)₂]₂ and chiral diene ligands as benchmark reaction. To get access to Rh complexes of different polarity, enantiomerically pure C₂-symmetric p-substituted 3,6-diphenylbicyclo[3.3.0]octadienes 4 and diastereomerically enriched unsymmetric norbornadienes 5 and 6 carrying either the Evans or the SuperQuat auxiliary were synthesized. A microemulsion containing the equal amounts of H₂O/KOH and toluene/reactants was formulated using the hydrophilic sugar surfactant n-octyl β-d -glucopyranoside (C₈G₁) to mediate the miscibility between the nonpolar reactants and KOH, needed to activate the Rh–diene complex. Prominent features of this organized reaction medium are its temperature insensitivity as well as the presence of water and toluene-rich compartments with a domain size of 55 Å confirmed by small-angle X-ray scattering (SAXS). Although bicyclooctadiene ligands 4 a , b , e performed equally well under homogeneous and microemulsion conditions, ligands 4 c , d gave a different chemoselectivity. For norbornadienes 5 , 6 , however, microemulsions markedly improved conversion and enantioselectivity as well as reaction rate, as was confirmed by kinetic studies using ligand 5 b .     

Synthesis of 3′‐1,2,4‐triazolo‐ and 3′‐1,3,4‐thiadiazoliminothymidines

New 5′‐acetyl‐3′‐1,3,4‐thiadiazoliminothymidines 11, 14 were prepared, via spontaneous rearrangments, by cycloaddition of 5′‐acetyl‐3′‐deoxy‐3′‐isothiocyanatothymidine 9 with 1‐aza‐2‐azoniaallene hexachloantimonates. Similary, 3′‐cyano analogue 19 was reacted with the same cumulenes to furnish 3′‐1,2,4‐triazolo‐thymidines 22, 24 , and 26 . Deblocking of the acylated products afforded the free nucleosides. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:298–303, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10146     

A comprehensive study of optimization algorithm for wireless coverage in indoor area

Coverage optimization using minimum number of transmitters is critical to service providers and vendors that need to control the coverage as well as the huge costs involved. In this regards, an existing coverage algorithm for determining the minimum number of transmitting antennas as well as their appropriate locations to provide the optimized wireless coverage for indoor environment is studied in this paper. The algorithm uses ray-tracing to predict the signal distribution from the transmitter to the sampling points (receivers) and genetic algorithm to determine the minimum number of transmitters and their corresponding locations to achieve the optimum wireless coverage. The complexity and performance of the algorithm are also analyzed and it is found that it has exponentially increasing complexity of $2^{n}$ and the change of computation time is greater with small change of the number of receiving points. Moreover, under the multi-transmitter scenario (real case), the accuracy achieved by fading, coverage ability, and signal to noise ratio is in the range of 96–99 %.     

Rheological response and small-angle neutron-scattering study of diester-bonded cationic biodegradable gemini surfactants in presence of different additives

Morphological changes and internal packing arrangements of planar dicationic-ester-bonded biodegradable gemini surfactants ethane-1, 2-diyl-bis(N,N-dimethyl-N-alkylammonium acetoxy) dichlorides (m-E2-m) have been explored by exploiting small-angle neutron-scattering (SANS) measurements. The data have been analyzed on the basis of Hayter and Penfold model for macroion solutions to obtain information about the aggregation behavior at the molecular level. The extent of micellar growth and structural changes of the micelles formed by these surfactants have been found to depend on the number of methylene units in their tail length. The growth and variation of micellar shape are more pronounced for the surfactant with longer tail length (m?=?16), whereas the surfactants with shorter tail length showed less variation of these properties in aqueous solution. Semi-major axes of the micelles show flexibility while varying the concentration and temperature of the systems; however, semi-minor axes remain rigid. Changes in the structural parameters of the micelles with addition of different salts were also inferred from SANS measurements. The intensity of scattered neutrons at the low Q region was found to increase while varying the nature of salt from monovalent to trivalent. On the basis of rheological responses, the rich aggregation behavior resulting from the addition of sodium salicylate (NaSal) is attributed to the special molecular structure of the gemini surfactant and the appropriate interaction between the surfactant and NaSal. This is inferred on the basis of behavior observed by varying the chain length (m) of the gemini surfactant that resulted in the formation of different types of microstructures.     

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives

[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, π‐stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bio‐ and materials science. In the last few years, [2.2]paracyclophane chemistry has progressed tremendously, enabling the fine‐tuning of its structural and functional properties. This Minireview highlights the most important recent synthetic developments in the selective functionalization of PCP that govern distinct features of planar chirality as well as chiroptical and optoelectronic properties. Special focus is given to the function‐inspired design of [2.2]paracyclophane‐based π‐stacked conjugated materials by transition‐metal‐catalyzed cross‐coupling reactions. Current synthetic challenges, limitations, as well as future research directions and new avenues for advancing cyclophane chemistry are also summarized.     

Investigation of thermo-reversibility of polymer crosslinked by reversible covalent bonds through torque measurement

Brominated butyl rubber (BIIR) was crosslinked through an esterification reaction using the sodium salt of dicyclopentadiene dicarboxylic acid (DCPDCA) as crosslinking agent. The crosslinked BIIR could de-crosslink upon heating and re-crosslink upon cooling due to Diels-Alder type reversible de-dimerization/re-dimerization of dicyclopentadiene moieties in the rubber networks. Torque measurement of the crosslinked rubber was conducted at various temperatures using a typical curemeter to investigate the thermo-reversibility. It was revealed that proper temperature for thermal processing of the crosslinked BIIR would be around 174 °C, at which the crosslinked polymer exhibits good flowability and is not too high to induce unexpected side reactions. The torque measurement was also carried out to investigate the efficiency of antioxidant on retarding the loss of the thermo-reversibility of the crosslinked polymer during heating-cooling cycles. It was found that addition of antioxidant 2246 [2,2′-methylenebis(6-tert-butyl-4-methylphenol)] into BIIR could significantly improve the thermo-reversibility of DCPDCA crosslinked BIIR. Torque measurement provides a convenient and sensitive method to understand the thermal behavior of reversible covalent crosslinked polymer.     

Synthesis of Novel Symmetric Porphyrin Schiff Base Dimers by Solid–Liquid Reaction Methodology

A new convenient solid–liquid condensation reaction procedure for the synthesis of novel asymmetric and symmetric meso‐tetraarylporphyrin and metalloporphyrin Schiff bases is reported. The condensation reaction between β‐formyl porphyrin or metalloporphyrins and aromatic amines was carried out at solid–liquid interface by using neutral alumina powder as a solid support for β‐formyl porphyrin or metalloporphyrins and absolute ethanol as the carrier solvent for aromatic amines. Six different asymmetric porphyrin/metalloporphyrin Schiff bases were synthesized via solid–liquid interface reaction methodology. The same solid–liquid synthetic methodology was applied for the synthesis of six novel symmetric Schiff base porphyrin/metalloporphyrin dimers. The comparison of UV–visible spectra of porphyrin Schiff base monomers and dimers revealed that some degree of electronic perturbation has occurred upon dimerization as the Soret bands of the monomers underwent peak broadening along with red shifts. Column chromatography and crystallization were used to purify the compounds. Fourier transform infrared, UV–visible, elemental analysis, ¹H NMR, and mass spectrometry were used to characterize the newly synthesized compounds.