Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

Experimental analysis, modeling, and theoretical design of McMaster pore-filled nanofiltration membranes

A side-by-side comparison of the performance of McMaster pore-filled (MacPF) and commercial nanofiltration (NF) membranes is presented here. The single-salt and multi-component performance of these membranes is studied using experimental data and using a mathematical model. The pseudo two-dimensional model is based on the extended Nernst–Planck equation, a modified Poisson–Boltzmann equation, and hydrodynamic calculations. The model includes four structural properties of the membrane: pore radius, pure water permeability, surface charge density and the ratio of effective membrane thickness to water content. The analysis demonstrates that the rejection and transport mechanisms are the same in the commercial and MacPF membranes with different contributions from each type of mechanism (convection, diffusion and electromigration). Solute rejection in NF membranes is determined primarily by a combination of steric and electrostatic effects. The selectivity of MacPF membranes is primarily determined by electrostatic effects with a significantly smaller contribution of steric effects compared to commercial membranes. Hence, these membranes have the ability to reject ions while remaining highly permeable to low molecular weight organics. Additionally, a new theoretical membrane design approach is presented. This design procedure potentially offers the optimization of NF membrane performance by tailoring the membrane structure and operating variables to the specific process, simultaneously. The procedure is validated at the laboratory scale.     

Long-Range proton-proton coupling constants. I. Propanic coupling involving a methyl group 4JMeH

An equation is formulated on the basis of theoretical INDO/FPT calculations which describes the angular dependence of the propanic long-range coupling constant ⁴J_MeH in substituted HCCCH₃ fragments. This equation is a truncated Fourier series in the torsion angle ?, HCCMe, which takes into account the dependence of the Fourier coefficients on the bond angle θ, CCMe. The substituent effects are assumed to be additive. Some parameters in the equation may be obtained from the ⁴J_MeH couplings in propane and neopentane derivatives. The calculated effect upon ⁴J_MeH of changes in the bond angle θ is significant and it seems to be in part the cause of some effects which have been attributed to conformational dependence.     

Algorithmic analysis of theMAP/PH/1 retrial queue

In this paper the distribution of the maximum number of customers in a retrial orbit for a single server queue with Markovian arrival process and phase type services is studied. Efficient algorithm for computing the probability distribution and some interesting numerical examples are presented.     

DEUSS: a perdeuterated poly(oxyethylene)-based resin for improving HRMAS NMR studies of solid-supported molecules

A novel resin called DEUSS (perdeuterated poly(oxyethylene)-based solid support) has been prepared by anionic polymerization of deuterated [D4]ethylene oxide, followed by cross-linking with deuterated epichlorohydrin. DEUSS can be suspended in a wide range of solvents including organic and aqueous solutions, in which it displays a high swelling capacity. As measured by proton HRMAS of the swollen polymer, the signal intensity of the oxyethylene protons is reduced by a factor of 110 relative to the corresponding nondeuterated poly(oxyethylene)poly(oxypropylene) (POEPOP) resin, thus facilitating detailed HRMAS NMR studies of covalently linked molecules. This 1H NMR invisible matrix was used for the solid-phase synthesis of peptides, oligoureas, and a series of amides as well as their characterization by HRMAS NMR spectroscopy. On-bead NMR spectra of high quality and with resolution comparable to that of liquid samples were obtained and readily interpreted. The complete absence of the parasite resin signals will be of great advantage, for example, for the optimization of multistep solid-phase stereoselective reactions, and for the conformational study of resin-bound molecules in a large variety of solvents.     

Effect of some organic solvents and acids on the laser-induced atomic fluorescence of tin in air-hydrogen flames

The effects of some organic solvents and acids on the atomic fluorescence of tin in air-hydrogen flames have been examined. Ketones and alcohols greatly reduced the florescence sensitivity in fuel rich air-hydrogen flame whereas organic acids generally enhanced the fluorescence signal. The depressive effect of organic solvents was found to be highly dependent on the fuel to oxidant ratio in the flame. An attempt has been made to explain these effects, on the basis of possible reactions occurring in the flame.On leave from Institute of Chemistry, University of the Punjab, Lahore 54590, PakistanOn leave from Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain     

Flexible ureasil hybrids with tailored optical properties through doping with metal nanoparticles

Hybrid organic-inorganic nanocomposites containing uniform distributions of metal nanoparticles have been prepared by mixing a preformed nanoparticle colloid with the precursors of a ureasil, prior to the sol-gel transition. These nanocomposites possess not only high optical quality and optical features dictated by the size and shape of the nanoparticle dopants but also a high degree of flexibility, which can largely enhance the range of applications in practical devices. The deposition of a uniform silica shell on the nanoparticle surface prior to the sol-gel transition was found to be required to maintain the colloidal stability during the process and, thus, to retain the optical properties in the final nanocomposite material. This method can be readily extended to other materials, such as semiconductor and magnetic nanoparticles.     

Derivative spectrophotometric determination of nickel using Br-PADAP

A major problem with spectrophotometric methods for nickel is cobalt interference, because many of the reagents for nickel also react with cobalt. In this work, the interference of cobalt in the determination of nickel using 2-(5-bromo-2-pyridylaxo)-5-diethylaminophenol (Br-PADAP) was eliminated by the use of derivative spectrophotometry, using the zero-crossing method for evaluation of the derivative signal. Br-PADAP reacts with nickel(II) in the presence of Triton X-100 to form a red complex with absorption maxima at 530 and 562 nm. The reactions parameters and the conditions for the measurements of the first-derivative signal were studied and the results demonstrated that using the derivative technique, Br-PADAP can be used for nickel determination with a selectivity higher than that of ordinary spectrophotometry and with a limit of detection of 0.2 ng ml(-1). The pH should be in the range 5.0-6.0 using an acetate buffer. The determination of nickel in the presence of cobalt was performed with conventional and derivative procedures, and the results demonstrated that only the derivative method should be used and, of the methods used for evaluation of the derivative signal, the zero-crossing method is the best. The proposed procedure was used for nickel determination in steels standards. The results demonstrated that the procedure has satisfactory accuracy and precision. Cobalt interference can be also eliminated by using dual-wave-length spectroscopy.     

Application of the pKa rule to synthesize salts of bezafibrate

ABSTRACT

Co-crystallization frequently employs forces such as hydrogen bonds, halogen bonds, and π-π stacking to assemble molecules in a multi-component crystal. In an effort to increase the strength of the intermolecular interaction between the anti-cholesterol drug bezafibrate (BEZA), a wastewater contaminant, and hydrogen-bond-acceptor molecules, we modified the pK_a values of the acceptors. Here, we describe the first series of salts incorporating BEZA and achieve a variety of supramolecular architectures including discrete assemblies, 1D chains, tapes, and 2D sheets. We discuss exceptions to the pK_a rule, and demonstrate that the presence of hydrogen-bond-donor atoms on the acceptor molecule supports salt formation.     

Actinide heterobimetallic oxides (Th, U): reduction studies

In our laboratories we have been studying the synthesis and reactivity of binary actinide and lanthanide intermetallic compounds. In this work, the air-oxidation of ThCu₂ and AnNi₂ (An = Th, U) was followed by thermogravimetry (TG) and the products were characterized by X-ray powder diffraction (XRD). The heterobimetallic oxides obtained are described by the formulas 2MO·ThO₂ (M = Cu, Ni) and 2NiO·UO₃. The thermogravimetric analysis under hydrogen of these heterobimetallic oxides show one mass loss for 2MO·ThO₂ and two mass losses for 2NiO·UO₃ over a wide range of temperature (293–1273 K). The characterization by XRD shows that the reduction products are 2M·ThO₂ (M = Cu, Ni) and 2Ni·UO₂, with all the actinides in the 4+ oxidation state. The actinide heterobimetallic oxides were described as copper or nickel supported catalysts.