Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

Reaction of 1,3-propanediol with the achiral spermine-bridged cyclophosphazene 1 at various molar ratios in THF gives a number of spiro-and ansa-derivatives that exhibit different stereogenic properties, viz. racemic, meso or achiral forms. As expected, spiro forms are preferred (giving mono-, di-, tri- and tetra-substitution), although significant amounts of mono- and di-substituted ansa derivatives also occur. A number of new structures have been characterized by NMR spectroscopy and X-ray crystallography in this work; mono-spiro 2, di-mono-ansa 6 and di-spiro/mono-ansa 8. The mono-ansa compound 3 was observed in solution by NMR spectroscopy but no evidence was found for the monospiro/monoansa 5, a necessary precursor of compound 8. The tri-spiro derivative 7 has been isolated and characterized by 31P NMR spectroscopy, whereas the structures of the di-monospiro 4 (meso) and tetra-spiro 9 have been characterized previously. The stereogenic properties of many of the products have been confirmed by X-ray crystallography and/or by 31P NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Although the starting compound 1 is achiral, it is found that unsymmetrically-substituted derivatives with 1,3-propanediol give racemic mixtures for the mono-spiro 2 and tri-spiro 7 derivatives, whereas symmetrically-substituted derivatives such as di-mono-ansa 6 and di-spiro/mono-ansa 8 are meso. It is found that care must taken in interpreting the 'splitting' of 31P NMR signals on addition of CSA in terms of 'chirality' of molecules, because some meso compounds give false positive results due to changes from A2X-like to A2B or ABX spin systems

Development and validation of a numerical tool for the simulation of the temperature field and infrared radiance rendering in an urban scene

International audienceWe present a numerical tool aimed at simulating infrared images of an urban environment, by solving the direct heat transfer problem, and then computing the radiance rendering at the sensor level. SOLENE (Cerma, Nantes) was coupled with two software packages developed at ONERA: SUSHI (Simulation in Urban Scene of Heat dIffusion) and MOHICANS (MOdélisation Hyperspectrale d'Images en entrée Capteur pour l'ANalyse et l'inversion du Signal) for realizing this task. SUSHI is also used for computing the surface temperatures: either a 1D model or a 2D model is used. We present the whole software chain, its validation by software and experimental analysis

Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part I : The (Li, Mg, Zn)/SPIR0(30203) derivatives

Syntheses and molecular structures of three metallated (Li, Zn, Mg) derivatives of the macrocycle-bearing cyclophosphazene N3P3Cl4 [HN---(CH2)3---O---(CH2)2---O---(CH2)3---NH] (coded as SPIRO 30203, 1) are reported. These three molecular structures reveal three different patterns of metal coordination. In compound 2 one of the two hydrogen atoms in SPIRO 3O2O3 is substituted by lithium generating a dimeric structure with pentacoordinated lithium centers. This structure is further stabilized by N---H hydrogen bonds. In 3 both hydrogen atoms of the macrocyclic loop are replaced by two zinc atoms through a cross-link metallation leading again to a dimeric molecule. In this compound the Zn atom is found to be in a trigonal bipyramidal environment with one very long N---Zn interaction. The origin of the dimerization of the magnesium compound 4 is analogous to 3. Magnesium is in the center of a distorted octahedron, coordinated with the O- and N-donors of the macrocyclic loop and also one nitrogen atom of the N3P3 ring. 4 is the first example of a metallic center coordinated by a neutral phosphazene ligand. Typical metal-N and metal-O distances are (in Å): Li-O, 2.05—2.07; Li-N, 2.07—2.36; Zn-O, 2.08—2.14; Zn---N, 1.94—1.95 (2.49); Mg---O, 2.09—2.14; Mg---N, 2.07—2.31

Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part II : The (Al) /SPIRO (30203) derivatives

Synthesis and molecular structures of two metallated (aluminium) derivatives, [C9H19Cl4AlN5O2P3]· 1.5C7H8 and [C8H16Cl5AiN5O2P3] · 1.5C7H8, of the macrocycle-bearingcyclophosphazene N3P3Cl4 [HN--- (CH2)3---O---(CH2)2---O---(CH2)3-NH] (coded as SPIRO 30203) are reported. These two molecular structures reveal the same pattern of metal coordination where the two hydrogen atoms in SPIRO 30203 are substituted by aluminium generating monomeric structures with pentacoordinated aluminium centres in the inner cavities. In the first compound the exocyclic ligand at aluminium is a methyl group, in the second a chlorine atom. Typical Al---N, Al---O and Al-X distances are (Å):1.84-1.89, 1.97-2.04 and 1.93 in the former, 1.81-1.86, 1.93-2.01 and 2.12 in the latter, respectively

Prioritizing investments in innovations to protect women from the leading causes of maternal death

PATH, an international nonprofit organization, assessed nearly 40 technologies for their potential to reduce maternal mortality from postpartum hemorrhage and preeclampsia and eclampsia in low-resource settings. The evaluation used a new Excel-based prioritization tool covering 22 criteria developed by PATH, the Maternal and Neonatal Directed Assessment of Technology (MANDATE) model, and consultations with experts. It identified five innovations with especially high potential: technologies to improve use of oxytocin, a uterine balloon tamponade, simplified dosing of magnesium sulfate, an improved proteinuria test, and better blood pressure measurement devices. Investments are needed to realize the potential of these technologies to reduce mortality

Effect of pulsed delivery and bouillon base on saltiness and bitterness perceptions of salt delivery profiles partially substituted with KCl

Reducing salt levels in processed food is an important target for a growing numbers of food manufacturers. The effects of pulsed delivery (Dynataste) and bouillon base on saltiness and bitterness perception of partially substituted solutions (KCl) were investigated. Pulsed delivery did not enhance salt perception and resulted in greater Overall Bitterness Scores for the same level of substitution with KCl. The presence of the bouillon base masked to a certain extent the loss of saltiness induced by the substitution and resulted in lower Overall Bitterness Scores of the substituted profiles

Gene expression during bacterivorous growth of a widespread marine heterotrophic flagellate

Phagocytosis is a fundamental process in marine ecosystems by which prey organisms are consumed and their biomass incorporated in food webs or remineralized. However, studies searching for the genes underlying this key ecological process in free-living phagocytizing protists are still scarce, in part due to the lack of appropriate ecological models. Our reanalysis of recent molecular datasets revealed that the cultured heterotrophic flagellate Cafeteria burkhardae is widespread in the global oceans, which prompted us to design a transcriptomics study with this species, grown with the cultured flavobacterium Dokdonia sp. We compared the gene expression between exponential and stationary phases, which were complemented with three starvation by dilution phases that appeared as intermediate states. We found distinct expression profiles in each condition and identified 2056 differentially expressed genes between exponential and stationary samples. Upregulated genes at the exponential phase were related to DNA duplication, transcription and translational machinery, protein remodeling, respiration and phagocytosis, whereas upregulated genes in the stationary phase were involved in signal transduction, cell adhesion, and lipid metabolism. We identified a few highly expressed phagocytosis genes, like peptidases and proton pumps, which could be used to target this ecologically relevant process in marine ecosystems