Nanotubes of mixed-valence, transition metal compounds synthesized by solution phase approach

A solution-phase approach to synthesize four kinds of mixed-valence, transition metal compounds nanotube is described. The approach is based on the self-assembly of siloxane sol. The resulted production of mixed-valence, transition metal compounds share a common structural characteristic of tubular geometrical morphology, at least for the ones we studied. The results demonstrate that the synthesis strategy can be a general route for preparation of compound nanotubes. In addition, the size control of nanotubular materials can be easily achieved through varying the ionic strength of solution. Based on the strategy, the diameters of ultrathin Ru-Fe nanotubes can be easily tuned between 100 nm and 800 nm.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

A convergent solution-phase synthesis of the macrocycle Ac-Phe-[Orn-Pro-D-Cha-Trp-Arg], a potent new antiinflammatory drug

Relatively few cyclic peptides have reached the pharmaceutical marketplace during the past decade, most produced through fermentation rather than made synthetically. Generally, this class of compounds is synthesized for research purposes on milligram scales by solid-phase methods, but if the potential of macrocyclic peptidomimetics is to be realized, low-cost larger scale solution-phase syntheses need to be devised and optimized to provide sufficient quantities for preclinical, clinical, and commercial uses. Here, we describe a cheap, medium-scale, solution-phase synthesis of the first reported highly potent, selective, and orally active antagonist of the human C5a receptor. This compound, Ac-Phe[Orn-Pro-D-Cha-Trp-Arg], known as 3D53, is a macrocyclic peptidomimetic of the human plasma protein C5a and displays excellent antiinflammatory activity in numerous animal models of human disease. In a convergent approach, two tripeptide fragments Ac-Phe-Orn-(Boc)-Pro-OH and H-D-Cha-Trp(For)-Arg-OEt were first prepared by high-yielding solution-phase couplings using a mixed anhydride method before coupling them to give a linear hexapeptide which, after deprotection, was obtained in 38% overall yield from the commercially available amino acids. Cyclization in solution using BOP reagent gave the antagonist in 33% yield (13% overall) after HPLC purification. Significant features of the synthesis were that the Arg side chain was left unprotected throughout, the component Boe-D-Cha-OH was obtained very efficiently via hydrogenation Of D-Phe with PtO2 in TFA/water, the tripeptides were coupled at the Pro-Cha junction to minimize racemization via the oxazolone pathway, and the entire synthesis was carried out without purification of any intermediates. The target cyclic product was purified (>97%) by reversed-phase HPLC. This convergent synthesis with minimal use of protecting groups allowed batches of 50100 g to be prepared efficiently in high yield using standard laboratory equipment. This type of procedure should be useful for making even larger quantities of this and other macrocyclic peptidomimetic drugs.

Growth of Nanometric Gold Particles in Solution Phase

The time evolution of colloidal gold particles in the nanometric regime has been investigated by employing electron microscopy and electronic absorption spectroscopy. The particle size distributions are essentially Gaussian and show the same time dependence for both the mean and the standard deviation, enabling us to obtain a time-independent universal curve for the particle size. Temperature dependent studies show the growth to be an activated process with a barrier of about 18 kJ mol(-1). We present a phenomenological equation for the evolution of particle size and suggest that the growth process is stochastic.

Activities in the spinel solid solution, phase equilibria and thermodynamic properties of ternary phases in the system Cu Fe O

A review of the structural and thermodynamic information and phase equilibria in the Cu-Fe-O system suggested that a consistent, quantitative description of the system is hampered by lack of data on activities in the spinel solid solution CuFe2O4-Fe3O4. Therefore the activity of Fe3O4 in this solid solution is derived from measurements of the oxygen potentials established at 1000°C by mixtures containing Fe2O3 and spinel solid solutions of known composition. The oxygen pressures were measured manometrically for solid solutions rich in CuFe2O4, while for Fe3O4-rich compositions the oxygen potentials were obtained by an emf technique. The activities show significant negative deviations from Raoult’s law. The compositions of the spinel solid solutions in equilibrium with CuO + CuFeO2 and Cu + CuFeO2 were obtained from chemical analysis of the solid solution after magnetic separation. The oxygen potential of the three-phase mixture Cu + CuFeO2 + Fe3O4(spinel s.s.) was determined by a solid oxide galvanic cell. From these measurements a complete phase diagram and consistent thermodynamic data on the ternary condensed phases, CuFeO2 and CuFeO2O4, were obtained. An analysis of the free energy of mixing of the spinel solid solution furnished information on the distribution of cations and their valencies between the tetrahedral and octahedral sites of the spinel lattice, which is consistent with X-ray diffraction, magnetic and Seebeck coefficient measurements.

A Multi-phase Approach for Improving Information Diffusion in Social Networks

For maximizing influence spread in a social network, given a certain budget on the number of seed nodes, we investigate the effects of selecting and activating the seed nodes in multiple phases. In particular, we formulate an appropriate objective function for two-phase influence maximization under the independent cascade model, investigate its properties, and propose algorithms for determining the seed nodes in the two phases. We also study the problem of determining an optimal budget-split and delay between the two phases.

Solution-phase exfoliation of graphite for ultrafast photonics

We exfoliate graphite in both aqueous and non-aqueous environments through mild sonication followed by centrifugation. The dispersions are enriched with monolayers. We mix them with polymers, followed by slow evaporation to produce optical quality composites. Nonlinear optical measurements show similar to 5% saturable absorption. The composites are then integrated into fiber laser cavities to generate 630 fs pulses at 1.56 mu m. This shows the viability of solution phase processing for graphene based photonic devices. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Controlled synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes

The synthesis of monodisperse nanocrystals is an important topic in the field of nanomaterials not only for practical applications, but also for scientific interest in fundamental research. In this feature article, we mainly focus on synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes, and report some progress made recently in the observation and understanding of nucleation and growth of semiconductor nanocrystals. Firstly, a novel two-phase approach to monodisperse nanocrystals, which is different from the well-established synthesis models, is discussed. We demonstrate that the two-phase approach has a quite lengthy nucleation process, and can be applied to the synthesis of many kinds of binary monodisperse nanocrystals.

Controllable synthesis of highly luminescent and monodisperse CdS nanocrystals by a two-phase approach under mild conditions

Highly luminescent and monodisperse CdS nanocrystals (see Figure) have been synthesized using a two-phase approach. The synthesis of CdS nanocrystals at the liquid-liquid interface was easy, safe, and highly reproducible, and the reaction conditions were mild and controllable.

Solution-phase synthesis of Au@ZnO core-shell composites

A novel solution-phase method for the preparation of Au@ZnO core-shell composites was described. With this method, the composites were grown without heating that is usually needed in other solution methods. Atomic force microscopy (AFM) results show that the diameter of Au@ZnO core-shell composites is about 10.5 nm. X-ray photoelectron spectroscopy (XPS) was applied to characterize Au@ZnO core-shell composites. The optical properties of Au@ZnO core-shell composites, including UV-vis absorption and photo luminescence (PL), were observed at room temperature.

Fast, copper-free click chemistry: a convenient solid-phase approach to oligonucleotide conjugation

Solid-phase oligonucleotide conjugation by nitrile oxide-alkyne click cycloaddition chemistry has been successfully demonstrated; the reaction, compatible with all nucleobases, requires no metal catalyst and proceeds under physiological conditions.

One-Pot, High-Yield Synthesis of Convex Au Octahedra by H2O2 - Mediated Process In Solution Phase

A simple, non-seeding and high-yield synthesis of convex gold octahedra with size of ca. 50 nm in aqueous solution is described. The octahedral nanoparticles were systematically prepared by reduction of HAuCl4 using ascorbic acid (AA) in the presence of cetyltrimethylammonium bromide (CTAB) as the stabilizing surfactant while concentrations of Au3+ were fixed. The synthesizing process is especially different to other wet synthesis of metallic nanoparticles because it is mediated by H2O2. Mechanism of the H2O2 – mediated process will be described in details. The gold octahedra were shown to be single crystals with all 8 faces belonging to {111} family. Moreover, the single crystalline particles also showed attractive optical properties towards LSPR that should find uses as labels for microscopic imaging, materials for colorimetric biosensings, or nanosensor developments.