Chemoselective hydrogenation catalysts: Pt on mesostructured CeO2 nanoparticles embedded within ultrathin layers of SiO2 binder

Pt on mesostructured CeO(2) nanoparticles embedded within ultrathin layers of highly structured SiO(2) binder shows highest activity reported with 80% selectivity for the chemoselective hydrogenation of crotonaldehyde. Characterization by transmission electron microscopy (TEM), CO adsorption, and X-ray photoelectron spectroscopy (XPS) show the presence of small Pt metal particles, preferentially located on CeO(2) (70%) together with the formation of Pt-CeO(2-x) sites at the interface between Pt and CeO(2) (4 nm) nanoparticles. These sites are able to polarize the carbonyl group and facilitate the selective hydrogenation of this with respect to the double bond.     

Studies on the Oral Anticancer Drug JM-216: Synthesis and Characterization of Isomers and Related Complexes

The complex cis,trans,cis-[PtCl(2)(OAc)(2)NH(3)(c-C(6)H(11)NH(2))] (JM-216) is currently undergoing clinical evaluation as an antitumor agent. In support of characterization and analysis of this complex a study of its isomers and other complexes [PtCl(m)()(OAc)((4)(-)(m)()())NH(3)(c-C(6)H(11)NH(2))] (m = 0-4) has been undertaken. The complexes have been obtained by a variety of synthetic routes which now extend the scope for the preparation of platinum(IV) antitumor complexes. As platinum(IV) complexes are very stable to substitution in the absence of catalysis, use has been made of both light and base catalysis to promote substitution. Oxidative addition to platinum(II) using hypervalent iodine reagents has also been used. The stereochemistry of the complexes has been confirmed by spectroscopic studies, primarily NMR including natural abundance (15)N NMR spectroscopy.     

Synthetic entries to 6-fluoro-7-substituted indole derivatives

Three practical synthetic entries of functionalized 6-fluoro-7-substituted indole derivatives were developed in connection with the preparation of 7-fluoro-8-substituted-1,3,4,9-tetrahydropyrano[3,4-b]indole-1-acetic acid derivatives 11 . The first route, which permits group modification about position 8 of the pyranoindole skeleton, employs 2-bromo-3-fluoroaniline ( 18 ) as a key intermediate, the preparation of which was achieved by either a novel ortho metalation of 15 or via the intermediacy of 22 . The second route utilizes 32 to append a terminally functionalized three carbon side chain onto the indole template and in addition leads to 43 from 40 . The third route to the 7-fluoro-8-substituted-pyranoindole skeleton complements route two in that the synthetic pathway exploits 32 in a nucleophilic fashion to construct a terminally functionalized two carbon appendage onto the indole nucleus.     

Liquid chromatographic analysis of vitamin B6 in reconstituted infant formula: collaborative study

A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials.     

Seasonal and chemotype influences on the chemical composition of Lantana camara L.: Essential oils from Madagascar

Yellow-orange and pink-violet colours of flower plants of Lantana camara from Madagascar were studied with a focus on essential oil (EO) in order to characterize chemotype EO variability. The chemical composition of 73 samples of aerial part EO of L. camara collected each month of the year, at various location, have been characterized by gas chromatography-mass spectrometry (GC-MS). Among the 50 peaks characterized, 43 were identified. The main components changed within the two flower colour types. EO from yellow-orange colour of flowers compared to pink-violet flowers is characterized by high content in terpenic compounds and lower amount in oxygenated compounds. Similar results were observed during seasons, showing that the chemical composition is relatively stable all year long. The components characterizing the pink-violet flower chemotype are: sabinene (9.4-11.3%), 1,8-cineole (3.7-4.6%), linalool (4.8-6.1%), β-caryophyllene (11.3-13.6%), α-humulene (4.4-5.2%), β-bisabolene (1.7-2.3%), γ-cadinene (0.1-0.4%), ar-curcumene (1.0-1.6%), caryophyllene oxide (1.2-0.7%) and davanone (22.6-25.9%). The components characterizing the yellow-orange flower chemotype are: sabinene (9.0-14.3%), 1,8-cineole (0.8-1.0%), linalool (0.4-1.4%), β-caryophyllene (25.8-30.8%), α-humulene (2.4-2.6%), β-bisabolene (13.6-14.9%), γ-cadinene (0.6-5.2%), ar-curcumene (0.7-2.8%), caryophyllene oxide (0.1-0.4%) and davanone (0.0-0.6%). Chemical composition of nine L. camara industrial EO show that they are composed of mixture of yellow-orange and pink-violet colour of flower chemotypes. Davanone is found in all samples with a mean of 12.4%, linalool (5.4%) and 1,8-cineole (4.1%). For sesquiterpenes, the main are β-caryophyllene (15.9%), β-bisabolene (1.8%) and γ-muurolene (1.4%).     

Lattice systems with a continuous symmetry

We consider perturbations of a massless Gaussian lattice field on ? ^d ,d≧3, which preserves the continuous symmetry of the Hamiltonian, e.g., $$ - H = \sum\limits_{< x,y > } {(\phi _x - \phi _y )^2 + T(\phi _x - \phi _y )^4 ,\phi _x \in \mathbb{R}.} $$ It is known that for allT>0 the correlation functions in this model do not decay exponentially. We derive a power law upper bound for all (truncated) correlation functions. Our method is based on a combination of the log concavity inequalities of Brascamp and Lieb, reflection positivity and the Fortuin, Kasteleyn and Ginibre (F.K.G.) inequalities.     

Un théorème de représentation pour les martingales discontinues

We consider a fixed integer-valued random measure (also called a random point process). We represent any local martingale as the sum of a stochastic integral with respect to this random measure, and of a local martingale which does not jump on the support of the random measure.     

Is bismuth subsalicylate an effective nontoxic catalyst for plga synthesis?

Poly(d,l ‐lactide‐co‐glycolide) (PLGA) copolyesters are commonly used in biomedical applications. Researches were carried out on nontoxic or low‐toxic catalysts that are enough efficient to provide short polymerization times, adequate microstructure chains and similar properties than the commercial PLGA materials. In this study, PLGA were synthesized by ring‐opening copolymerization (ROP) using three different catalysts. Stannous octoate is the first catalyst we used, as it is very efficient, even its toxicity is still on debate. Two others low‐toxic catalysts [zinc lactate and bismuth subsalicylate (BiSS)] were also evaluated. The comparison of these ROP was realized in terms of kinetics and control of the polymerization. Then, the influence of the catalyst on the PLGA microstructure chains is reported. Finally, abiotic hydrolytic degradation rate is studied. Results described in this article show that BiSS is one very attractive catalyst to produce low toxic PLGA for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1130–1138     

Organic Syntheses Without Solvent: Preparation of Alkoxyphthalimides and of Alkoxylamines

Alkoxyphthalimides are prepared by alkylation of N-hydroxyphthalimide under solid-liquid phase transfer catalysis without solvent. When conversion of alkoxyphthalimides into alkoxylamines is nearly complete, neat hydrazine hydrate is added at room temperature.