Design of metal oxide nanoparticles: Control of size,shape, crystalline structure and functionalization by aqueous chemistry

The aim of this paper is to show that a very simple but well controlled chemistry in an aqueous medium allows one to efficiently control the main characteristics of oxide nanoparticles. Examples concerning titania, alumina, iron and manganese oxides are discussed to illustrate various effects on the control of size, shape and structure of nanoparticles. Some examples of functionalization of these particles are also illustrated. Experimental data, procedures and detailed references can be found in the cited literature.     

Newton's method on Riemannian manifolds and a geometric model for the human spine

To study a geometric model of the human spine we are led tofinding a constrained minimum of a real valued function definedon a product of special orthogonal groups. To take advantgeof its Lie group structure we consider Newton's method on thismanifold. Comparisons between measured spines and computed spinesshow the pertinence of this approach.     

Photoinduced formation of a cryptand from a coronand: an unexpected switch in cation binding affinity

Aza-crown ethers 2 and 3 with anthracene-containing pendant arms have been synthesised and characterised. Both compounds bind Group 1 metal cations in solution, forming complexes of 1:1 stoichiometry. The properties of compound 2 and its complexes have been studied by a range of techniques, including NMR, UV and fluorescence spectroscopy and X-ray crystallography. The pendant arms can adopt either a cis or a trans geometry, the cis geometry favoured with larger cations. The geometry of the complex affects the fluorescence properties of the system, with larger cations giving higher excimer/monomer ratios. Upon irradiation at lambda>300 nm, coronand 2 forms the cryptand 5 through a reversible intramolecular [4pi+4pi] cycloaddition reaction. The rates of the forward and reverse reactions of this photochromic process are cation dependent; in particular the rate of the thermal reverse reaction is decreased by smaller cations and increased by larger cations, especially Rb(+). The metal binding constants in methanol for 2 and 5 have been determined, revealing that the cryptand 5 binds Na(+) and Rb(+) more weakly than crown ether 2 by over two orders of magnitude.     

An efficient synthesis of the new benzo[c]pyrido[2,3,4-kl]acridine skeleton

A series of molecules of therapeutic interest, possessing the new skeleton of 1H-benzo[c]pyrido[2,3,4-kl]acridine with acyl or aminoacyl and methoxy or aminoalkoxy substituents on the aromatic homocycles were synthesized by means of a Friedl?nder-type reaction. The requisite 5-aminodihydroquinoline-4-ones 1, whose preparation is described, were reacted with the appropriate alpha-tetralones 2 using an acidic catalyst (PPTS) under azeotropic conditions. Optimized reaction time and yield depend on temperature, which must not be below 90 degrees C.     

Reactions of Metal Salts and Alkali Metal Nitrates. Role of the Metal Precursors and Alkali Metal Ions in the Resulting Phase of Zirconia

Zirconia powders are prepared by reaction of a zirconium precursor with an alkali metal nitrate. The major part of the reactions takes place before the melting points and then the reactions go slowly to completion at 450°C in the molten salts. The roles of the precursor and the alkali metal ion are discussed considering the reaction between two precursors, octahydrated zirconium oxychloride and zirconium tetrachloride, and two nitrates, LiNO₃ and NaNO₃, and some resulting physico-chemical differences. The obtained zirconia powders contain very small amounts of alkali metal ions which act as stabilizing agent. Their effect on the balance tetragonal-monoclinic ZrO₂ depends upon the homogeneity of their distribution which is related to their ability to diffuse inside the bulk of particles and their polarizing power when located mainly on the surface.     

The specific contribution of phosphorus in dendrimer chemistry

Besides properties commonly found for all types of dendrimers, phosphorus-containing dendrimers possess some specific properties seldom or never found for other types of dendrimers. Emphasis will be put on these specificities.     

A new supramolecular assembly obtained from the combination of silver(I) cations with a thiophosphorylated cavitand

The new tetra-thiophosphonatocavitand 1 in its iiii configuration extracts quantitatively Ag+ ions from aqueous solutions; the tetranuclear complex [1(2).Ag4Pic4] was selectively formed and characterized in the solid state by X-ray diffraction which revealed the formation of a new dimeric assembly through Ag+ coordination.     

Expression of the prohelicity of bis-cyclomanganated 2,3-diphenylquinoxaline through reactions with diaryldiazomethanes

The reactions of bis-cyclomanganated 2,3-diphenylquinoxaline with diazodiphenylmethane and 9-diazofluorene allowed the formation of a new oligomeric and dinuclear manganospiralene and the ready preparation of a pentacyclic helix comprising two (eta 5-fluorenyl)Mn(CO)3 fragments, whose helicity can be locked upon one-dimensional linear coordination to silver cation.     

Bis(isoquinoline N-oxide) pincers as a new type of metal cation dual channel fluorosensor

[structure: see text] A new type of donor-spacer-acceptor podand system has been synthesized and proved as an efficient dual channel fluorosensor for Li+, Mg2+, and Ca2+. The known ability for the N-oxide function to bind Lewis acids is the key step in the appearance of a new emitting charge-transfer (CT) excited state. The occurrence of this CT state for alkaline earth (Mg2+ and Ca2+) and not for alkaline metals (Li+) provided a new type of dual channel fluorosensors.     

Milliwatt-peak-power pulse characterization at 1.55 microm by wavelength-conversion frequency-resolved optical gating

A novel wavelength-conversion configuration based on four-wave mixing in an optical fiber has been used to generate a frequency-resolved optical gating (FROG) trace identical to that obtained from second-harmonic generation (SHG). The use of an optical fiber waveguide permits enhanced measurement sensitivity compared with that of conventional SHG-FROG and has been used for complete characterization of 1-mW peak-power picosecond pulses at 1.55 microm from an unamplified semiconductor laser diode gain switched at 10 GHz.