Modeling shell formation in core-shell nanocrystals in reverse micelle systems

The mechanisms responsible for the formation of the shell in core-shell nanocrystals are ion-displacement and heterogeneous nucleation. In the ion-displacement mechanism, the shell is formed by the displacement reaction at the surface of the core nanoparticle whereas in heterogeneous nucleation the core particle induces the nucleation (or direct deposition) of shell material on its surface. The formation of core-shell nanocrystals via the post-core route has been examined in the current investigation. A purely probabilistic Monte Carlo scheme for the formation of the shell has been developed to predict the experimental results of Hota et al. (Hota, G.; Jain, S.; Khilar, K. C. Colloids Surf., A 2004, 232, 119) for the precipitation of Ag2S-coated CdS (Ag2S@CdS) nanoparticles. The simulation procedure involves two stages. In the first stage, shell formation takes place as a result of the consumption of supersaturation, ion displacement, and reaction between Ag+ and excess sulfide ions. The growth in the second stage is driven by the coagulation of nanoparticles. The results indicate that the fraction of shell deposited by the ion-displacement mechanism increases with increasing ion ratio and decreases with increasing water-to-surfactant molar ratio.     

Towards a comprehensive 2-D-LC-MS separation

A comprehensive 2-D-LC-MS method has been developed by coupling columns of different selectivity. The primary column eluate is alternately trapped and sampled onto the secondary columns through a guard column interface. When one guard column traps the eluate, the other injects the previously trapped components onto a secondary column. This cycle is repeated throughout the chromatogram. The use of dual secondary columns provides the secondary columns with additional time to generate high-speed chromatograms. Each secondary column generates alternate chromatograms which when combined generate the entire chromatogram. The primary column separation is comparable to conventional HPLC, whereas the secondary column separation is fast. With both the columns operating in reverse phase mode, one would expect strong correlation in the two-dimensional retention and hence inefficiency in separation. However, differences in column operation modes, interaction mechanisms, and vendor silica result in a complementary separation. The system was evaluated by comparing it to one-dimensional counterparts and coupled column chromatography. Although some correlations were observed in 2-D-LC-MS, peaks do show two-dimensional distribution with superior UV and MS data as co-elution is minimized. Also, the ease of converting conventional systems to 2-D-LC-MS is discussed.     

Spectroscopic,structural and magnetic studies of nickel(II) complexes with tetra- and pentadentate ligands

Abstract  Two new nickel(II) complexes, namely [Ni(BPSE)](BF₄) 1, and [Ni (5-BST)CH₃OH]ClO₄ 2 [BPSE = 2-benzoylpyridinesalicylidene ethylenediamine, 5-BST = 5-bromosalicylidene-tris(2-aminoethyl)amine] have been synthesized and characterized using various physico-chemical methods. The magnetic and spectroscopic data indicate a distorted square planar geometry for complex 1, while complex 2 is assigned a distorted octahedral geometry. Complex 1 crystallized in the triclinic space group P-1. Complex 2 adopts an octahedral geometry with space group symmetry P 21/n. The superoxide dismutase activity of these complexes has been measured. Graphical Abstract  This paper describes three new nickel (II) complexes viz; [Ni(BPSE)](BF4) 1, [Ni(BSE)] 2 and [Ni (5-BST) CH3OH] ClO4 3 [BPSE = 2-benzoylpyridine salicyledene-ethylenediamine, BSE = bis(salicylaldehyde) ethylenediamine, 5-BST = 5-bromosalicyledene-tris(2-amino ethyl) amine]. The magnetic and spectroscopic data indicate a distorted square planar geometry for complex 1 and 2, while the comlplex 3 is assigned a distorted octahedral geometry. Superoxide dismutase activity of these complexes have also been measured. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Second order duality for nondifferentiable multiobjective programming problem involving (F, α, ρ, d)-V-type I functions

In this paper, new classes of second order (F, α, ρ, d)-V-type I functions for a nondifferentiable multiobjective programming problem are introduced. Furthermore, second order Mangasarian type and general Mond-Weir type duals problems are formulated for a nondifferentiable multiobjective programming problem. Weak strong and strict converse duality theorems are studied in both cases assuming the involved functions to be second order (F, α, ρ, d)-V-type I.     

Kinetic studies on the aminolysis of O-(2,4-dinitrophenyl)-cyclopentanone oxime in benzene

The reaction of O-(2,4-dinitrophenyl) cyclopentanone oxime with four primary alkylamines and a secondary arylamine, pyrrolidine, in benzene has been investigated. In pyrrolidinolysis, a third order dependence on [amine] has been observed, which has been explained on the basis of a cyclic transition state. The aminolysis with primary alkyl amines shows a normal dependence of second order on [amine].

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O-(2,4-) - . , . .

     

High power and high efficiency green light emitting diode on free‐standing semipolar (11$ \bar 2 $2) bulk GaN substrate

We demonstrate a high power green InGaN/GaN multiple‐quantum‐well (MQW) light emitting diode (LED) with a peak emission wavelength of 516 nm grown on low extended defect density semipolar (11 2) bulk GaN substrate by metal organic chemical vapor deposition. The output power and external quantum efficiency (EQE) at drive currents of 20 and 100 mA under direct current (DC) operation were 5.0 mW, 10.5% and 15.6 mW, 6.3%, respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparative chemical fingerprinting of Oroxylum indicum and Scutellaria baicalensis using liquid chromatography and mass spectrometry

Introduction: Identification of Oroxylum indicum and Scutellaria baicalensis provides an interesting challenge in selection of biomarker compound to be used in routine analysis. Both plants have similar phytochemical profile and are rich sources of flavones and flavone glycosides. The objective of this study was to prepare the chemical fingerprinting of O. indicum bark and S. baicalensis roots using the liquid chromatography and mass spectroscopy in single chromatographic method. Materials and methods: Extracts prepared using various solvent systems (methanol, aqueous methanol, chloroform, hexane, and water) of both plants were analyzed using C18 reverse phase column with solvent system containing acetonitrile and 0.1% formic acid. Major flavonoids were identified based on mass spectra, fragmentation pattern, and UV spectra. Results: In this article, well-resolved high-performance liquid chromatographic (HPLC) separation in both plant extracts was obtained and chemical fingerprints for both plant extracts were established and flavonoids present (baicalin, oroxylin A-7-O-glucuronide, chrysin-7-O-glucuronide, baicalein, chrysin, oroxylin-A, wogonin, skullcap flavone II) were identified as possible biomarkers. Conclusion: Mass spectrometry coupled with HPLC can be a tool for fingerprinting of various natural products used in dietary supplement industry. The fingerprint developed in the article can be used for quality evaluation as well as identifying possible adulteration of extracts of both the plants.     

Synthesis of iron oxide nanorods via chemical scavenging and phase transformations of intermediates at ambient conditions

Chemically induced shape transformations of isotropic seeds, comprised of iron oxyhydroxides and iron oxide borate into nanorods, is reported. Transient growth studies show that the nanorods are formed via phase transformation and aggregation of various metastable species. Addition of tetra-methyl-ammonium hydroxide (TMAH) to the in situ synthesized seeds ensures a typical reaction pathway that favors formation of magnetite (Fe ₃ O ₄) via the steps of chemical etching, phase transformation of intermediates, and crystal consolidation. Whereas, with addition of sodium hydroxide (NaOH), either magnetite (Fe ₃ O ₄) or a mixture of (γ-Fe ₂ O ₃ + α-FeOOH) is obtained. The shape with both the additives is always that of nanorods. When the seeds treated with TMAH were aged in an ultrasonication bath, rods with almost twice the length and diameter (length = 2800 nm, diameter = 345 nm) are obtained as compared to the sample aged without ultrasonication (length = 1535 nm, diameter = 172 nm). The morphology of nanostructures depending upon other experimental conditions such as, aging the sample at 60 ^°C, seeds synthesized under ultrasonication/ stirring or externally added are also examined and discussed in detail. All the samples show high coercivity and strong ferromagnetic behavior at room temperature and should be promising candidates as ferro-fluids for various applications.     

Robust penalty function method for an uncertain multi-time control optimization problems

This paper gives some new results on multi-time first-order PDE constrained control optimization problem in the face of data uncertainty (MCOPU). We obtain the robust sufficient optimality conditions for (MCOPU). Further, we construct an unconstrained multi-time control optimization problem (MCOPU)_? corresponding to (MCOPU) via absolute value penalty function method. Then, we show that the robust optimal solution to the constrained problem and a robust minimizer to the unconstrained problem are equivalent under suitable hypotheses. Moreover, we give some non-trivial examples to validate the results established in this paper.