Ultrastructural study of spermiogenesis and the spermatozoon of Cavisoma magnum (Southwell, 1927) (Acanthocephala, Palaeacanthocephala, Cavisomidae), from Siganus lineatus (Pisces, Teleostei, Siganidae) (Valenciennes, 1835) in New Caledonia

This paper presents an ultrastructural study of Cavisoma magnum (Acanthocephala, Cavisomatidae) with a Transmission Electron Microscopy tool. This parasite of the fish Siganus lineatus is here reported for the first time from off New Caledonia, South Pacific. It is the first study describing the ultrastructure, spermiogenesis and spermatozoon of a species of the family Cavisomatidae. The young spermatid of C. magnum possesses a centriole constituted of doublets without a central element. After the elaboration of a flagellum of 9+2 pattern, the centriole migrates in a nuclear groove. Then the flagellum migration occurs and gives rise to a spermatozoon. The distribution and the size of the protein granules are reported and the posterior extremity appears like a chromatin lamina wave. Comparative ultrastructural data are presented on sperm and spermiogenesis of the Acanthocephala and Rotifers examined to date and the phylogenetic implications are discussed.     

Heterocyclic lithium amides as chiral ligands for an enantioselective hydroxyalkylation with n-BuLi

Chiral heterocyclic structures based on 3-aminopyrrolidines (3APs), 3-aminotetrahydrothiophens (3ATTs), and 3-aminotetrahydrofurans (3ATFs) have been synthesized. The corresponding lithium amides have been evaluated as chiral ligands in the condensation of n-BuLi on o-tolualdehyde. The returned levels of induction were in the 46-80% ee range. The cheap and easily prepared 3ATFLi's turned out to be also the best ligands, giving access to the expected R or S alcohols in a same 80% level of induction at -78 degrees C in THF. In all cases, the sense of induction depends on the absolute configuration of C(8) on the 3-amino appendage. A general concept is proposed to rationalize the process of induction in the presence of organolithium species.     

Base-promoted rearrangement of cage α-haloketones—II : 12-oxa-3,5,9,10-tetrachlorohexacyclo[5.4.1.02,6.03,10.05,9.08,11]-dodecane-4-one

A synthesis of 12-oxa-3,5,9,10-tetrachlorohexacyclo[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]dodecane-4-one (6) from 4,4-dimethoxy-2,3,5,6-tetrachloropentacyclo [[5.4.0.0^2,6.0^3,10.0^5,9]undecane-8,11-dione (1) is described. Reaction of 6 with sodium hydroxide in refluxing benzene, toluene, or tetrahydrofuran affords 11-oxa-3,4,5-exo-6-tetrachloropentacyclo [[6.2.1.0^2,7.0^4,10.0^5,9]undecane-endo-3-carboxylic acid (7a, 80·2% yield). The corresponding reaction of 6 with refluxing aqueous sodium hydroxide solution affords 4,12-dioxa-8,11-dichlorohexacyclo-[5.4.1.0^2,6.0^3,10.0^5,9.0^8,11]dodecane-1-carboxylic acid (8a, 66·5% yield). A mechanism which accounts for the formation of 7a and 8a from 6 is presented.     

One-Pot Synthesis of Cage-Functionalized,Ketal-Containing Crown Ethers

Acid-catalyzed reaction of pentacyclo[5.4.0.0^2,6.0^3,10.0^5.9]undecane-8,11-dione (1) with penta(ethylene glycol) produced two cage-functionalized, ketal-containing crown ethers, i.e., 2 and 3, in low yield. The structure of 2 was established unequivocally by direct methods. Alkali metal picrate extraction data obtained for 2 and for a structurally related model compound, i.e., 18-crown-6,indicate that 2 is an inefficient alkali metal picrate extracting agent.     

Reactions Invariantes Induisant La Densification Des Varistances ZnO

The electrical properties of ZnO varistors are induced by a sintering step. The phenomena occurring during this thermal treatment have been studied through model systems whose nature and composition are well defined. The pure BiSbO₄ and Bi₃ Zn₂ Sb₃ O₁₄ phases have been synthetised by Direct Oxidation of a Precursory Alloy (DOPA) and characterized using XRD method. Each one of these phases can react with zinc monoxide through an invariant isobaric reaction in the ZnO–Bi₂ O₃ –Sb₂ O₃ system: – at 998°C 17/3<ZnO>+2/3<Bi₃ Zn₂ Sb₃ O₁₄ > arrow <Zn₇ Sb₂ O₁₂ > + ((Bi₂ O₃ )) – at 1058°C 7<ZnO>+2<BiSbO₄ > arrow <Zn₇ Sb₂ O₁₂ >+((Bi₂ O₃ )) These thermodynamic considerations can explain the thermal domain of the sintering reaction described in the literature. This revised version was published online in July 2006 with corrections to the Cover Date.     

A convenient route to functionalized 3-amino-N-methylfuro[3,2-b]pyridine-2-carboxamides

The synthesis of novel functionalized 3-amino-N-methylfuro[3,2-b]pyridine-2-carboxamides is described from cyanopyridine intermediates. Based on the difference in halogen reactivity, ethyl [(5-bromo-2-chloropyridin-3-yl)oxy]acetate was functionalized by a palladium-catalyzed reaction, before the cyclization to the desired furo[3,2-b]pyridines.     

Modifying polymer flocculants for the removal of inorganic phosphate from water

Due to strong hydrogen bonding interactions, thiourea has been shown to have a high affinity for anions such as inorganic phosphate. The interaction between phosphate and thiourea has been used to develop technologies that can detect and even remove phosphate from water. This research investigates the use of thiourea derivatized polymer flocculants for the sequestering of inorganic phosphate from water. The study presented herein describes the development of a thiourea based monomer that was used to create a bi-functional polymer that flocculates suspended solid material as well as sorbs phosphate, removing both from water. The new polymer removed more than 60% of the phosphate from a simulated wastewater sample. The addition of a thiourea trapping group to the polymer more than doubled the amount of phosphate removed from solution compared to control polymers.     

'Stealth' corona-core nanoparticles surface modified by polyethylene glycol (PEG): influences of the corona (PEG chain length and surface density) and of the core composition on phagocytic uptake and plasma protein adsorption

Nanoparticles possessing poly(ethylene glycol) (PEG) chains on their surface have been described as blood persistent drug delivery system with potential applications for intravenous drug administration. Considering the importance of protein interactions with injected colloidal dug carriers with regard to their in vivo fate, we analysed plasma protein adsorption onto biodegradable PEG-coated poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA) and poly(-caprolactone) (PCL) nanoparticles employing two-dimensional gel electrophoresis (2-D PAGE). A series of corona/core nanoparticles of sizes 160–270 nm were prepared from diblock PEG-PLA, PEG-PLGA and PEG-PCL and from PEG-PLA:PLA blends. The PEG Mw was varied from 2000–20 000 g/mole and the particles were prepared using different PEG contents. It was thus possible to study the influence of the PEG corona thickness and density, as well as the influence of the nature of the core (PLA, PLGA or PCL), on the competitive plasma protein adsorption, zeta potential and particle uptake by polymorphonuclear (PMN) cells. 2-D PAGE studies showed that plasma protein adsorption on PEG-coated PLA nanospheres strongly depends on the PEG molecular weight (Mw) (i.e. PEG chain length at the particle surface) as well as on the PEG content in the particles (i.e. PEG chain density at the surface of the particles). Whatever the thickness or the density of the corona, the qualitative composition of the plasma protein adsorption patterns was very similar, showing that adsorption was governed by interaction with a PLA surface protected more or less by PEG chains. The main spots on the gels were albumin, fibrinogen, IgG, Ig light chains, and the apolipoproteins apoA-I and apoE. For particles made of PEG-PLA45K with different PEG Mw, a maximal reduction in protein adsorption was found for a PEG Mw of 5000 g/mole. For nanospheres differing in their PEG content from 0.5 to 20 wt %, a PEG content between 2 and 5 wt % was determined as a threshold value for optimal protein resistance. When increasing the PEG content in the nanoparticles above 5 wt % no further reduction in protein adsorption was achieved. Phagocytosis by PMN studied using chemiluminescence and zeta potential data agreed well with these findings: the same PEG surface density threshold was found to ensure simultaneously efficient steric stabilization and to avoid the uptake by PMN cells. Supposing all the PEG chains migrate to the surface, this would correspond to a distance of about 1.5 nm between two terminally attached PEG chains in the covering ‘brush’. Particles from PEG5K-PLA45K, PEG5K-PLGA45K and PEG5K-PCL45K copolymers enabled to study the influence of the core on plasma protein adsorption, all other parameters (corona thickness and density) being kept constant. Adsorption patterns were in good qualitative agreement with each other. Only a few protein species were exclusively present just on one type of nanoparticle. However, the extent of proteins adsorbed differed in a large extent from one particle to another. In vivo studies could help elucidating the role of the type and amount of proteins adsorbed on the fate of the nanoparticles after intraveinous administration, as a function of the nature of their core. These results could be useful in the design of long circulating intravenously injectable biodegradable drug carriers endowed with protein resistant properties and low phagocytic uptake.