Solid state NMR characterization of formation of poly(ϵ‐caprolactone)/maghnite nanocomposites by in situ polymerization

Results of multinuclear MAS NMR spectroscopy are reported for poly (ε‐caprolactone)/maghnite nanocomposite formation, with ε‐caprolactone in situ polymerized in the presence of maghnite, a proton exchanged montmorillonite clay. Exfoliated and intercalated materials with different maghnite loading in the range 3–15 wt % were investigated. ¹H NMR evidences Brønsted acid hydroxyl groups in the silicate layers and shows that their broad signal at 7.6 ppm present in the parent clay disappears in the nanocomposite material. ²⁷Al MAS NMR results show that beside the hexacoordinated aluminum signal, two additional peaks corresponding to two different tetrahedral Al sites are present in the clay framework. The NMR signal intensity of only one of them was found to be affected in the nanocomposites compared with the parent maghnite, suggesting that these specific aluminum sites are the reactive ones at the initial stages of the polymerization. However almost no changes occurred in the ²⁹Si NMR spectra, confirming that the polymer grafting, as indicated earlier by atomic force microscopy, took place on the aluminum tetracoordinated sites rather than on the silicon sites. A mechanism of maghnite surface catalyzed polymerization of ε‐caprolactone was proposed, involving Brønsted and Lewis acid sites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3060–3068, 2007     

Pinacol-Pinacolone Rearrangement of 1, 2-Di-(p-methoxyphenyl)-ethane-1, 2-diol and Bis-(4-methoxyphenyl)-acetaldehyde in Acid Media

1, 2-Di-(p-methoxyphenyl)-ethane-1, 2-diol gave in acid media bis-(4-methoxy-phenyl)-acetaldehyde, 4-4′-dimethoxy-deoxybenzoin, and 1, 2-di-(p-methoxyphenyl)-ethylene oxide; their respective yields being influenced by at least 3 factors: (i) the acid, (ii) its concentration, and (iii) the reaction period. Bis-(4-methoxyphenyl)-acetaldehyde rearranged to the deoxybenzoin in boiling sulfuric (50%) or phosphoric (75%) acids (w/w), and to two isomeric 1, 2-diacetoxy-1, 2-di-(p-methoxyphenyl) ethanes when it was heated with acetic anhydride. The mechanisms of these reactions are discussed.     

Amperometric biosensors for glucose based on carbon paste modified electrodes

The modification of carbon-paste electrodes by incorporation of the enzyme glucose oxidase (GOD) is described. The resulting probes can be operated as amperometric glucose sensors in the presence or absence of a mediator (1,1'-dimethylferrocene) mixed into the paste. Extended linear calibration ranges have been obtained up to 90 and 5OmM glucose respectively. The electrode responses were rapid, reaching steady-state values within 30-40 sec. Advantages of using a GOD-paste formulation are suggested. Plasma glucose assays were correlated with spectrophotometric determinations based on glucose oxidase (y = 1.07x - 0.16, r = 0.973, n = 17).     

Synthesis of <Superscript>99m</Superscript>Tc-pefloxacin: A new targeting agent for infectious foci

Summary This investigation focused on the labeling of pefloxacin, a fluoroquinolone antibacterial agent, with ^99mTc to form ^99mTc-pefloxacin complex. The labeling process was done by direct addition of pertechnetate in isotonic solution to Sn-pefloxacin solution. The labeling technique is effective, as a high labeling yield (98%) was obtained after 30-minute reaction time. Different factors were found that influenced this labeling reaction: 0.5 mg pefloxacin or more must be used to prevent the formation of colloids in the reaction medium. Fifty micrograms of stannous chloride dihydrate were found to be sufficient to reduce all pertechnetate with activity ranging from 37 to 3700 MBq without the detection of free pertechnetate or colloids in the reaction mixture. The pH of the reaction medium was found to play an important role in the labeling process. The labeling reaction proceeds well at neutral pH (pH 6) but at acidic pH value (pH 4 or below) the yield of ^99mTc-pefloxacin complex decreased markedly to a labeling yield of 5%. The reaction mixture must be heated to 100 °C in an oil bath to enhance the formation of the ^99mTc-pefloxacin complex. The biodistribution data show that ^99mTc labeled pefloxacin was retained in infectious focus. The retention was specific since the abscess uptake of ^99mTc-pefloxacin remained high as compared to the uptake of aseptic foci at 24-hour post injection. Also, the clearance of the tracer from other tissues is rapid on the contrary to its clearance from the septic focus. This supports the hypothesis that ^99mTc-pefloxacin is retained at the infectious site because of its specific binding to the gyrase enzymes of bacterial cells.     

On simulations investigating droplet diameter–charge distributions in electrostatically atomized dielectric liquid sprays

A general procedure has been developed for the simulation of charged liquid and electrostatically atomized sprays. The procedure follows a Lagrangian approach for simulation of spray droplets and a Eulerian approach for gas‐phase variables, including the electric field generated by the charge presence on droplets. Validation of the procedure was examined through simulations of previously published charged spray experiments. Results showed that for the specification of initial droplet charge, modelling the droplet charge–diameter relationship through a scaling law is as reliable a method as using a directly obtained charge–diameter relationship from experimental measurements. The normalized root‐mean‐square errors for sprays using the two methods were shown to be within 12% of one another, for the prediction of spatially averaged profiles of mean droplet diameters, mean axial velocities and mean radial droplet velocities. Results showed that the general spatial characteristics and dynamics of a charged liquid spray can successfully be reproduced, including the axial and radial dispersal pattern of droplets and the distribution of mean droplet diameters throughout the spray plume. For all sprays with droplet charges defined through a scaling law relationship, the normalized root‐mean‐square errors range from 9.0% to 31.6% for mean droplet diameters, 10.4% to 67.9% for mean axial droplet velocities and 16.8% to 38.6% for mean radial droplet velocities. Lastly, we present a brief set of general recommendations for simulating electrostatically atomized dielectric liquid sprays.Copyright © 2013 John Wiley & Sons, Ltd.     

SYNTHESIS OF MONO-AND DIALKYLPHOSPHATES BY THE REACTIONS OF HYDROXYCOMPOUNDS WITH THE PHOSPHORUS PENTAOXIDE UNDER MICROWAVE IRRADIATION

The reactions of phosphorus pentoxide with two alcohols and one phenol were performed in different conditions under microwave irradiation. The products (alkylphosphates and dialkylphosphates) were identical to those formed by classic heating and were obtained with better yields. The speed of the reaction was increased by a factor from 100 to 4000.     

α,β-Unsaturated γ-Oxo Carboxylic Acids in Heterocylic Synthesis II. Behavior of 4-(5,5-Dioxodibenzothiophen-2-yl)-4-oxo-2-butenoic Acid Towards Carbon Nucleophiles under Michael Reaction Condition

4-(5,5-Dioxodibenzothiophen-2-yl)-4-oxo-2-butenoic acid ( 1 ) was condensed with compounds containing active methylene groups under Michael reaction conditions to form the Michael adducts 2a-c , 3a-c , and 4a-b . The behavior of Michael adduct towards the action of hydrazine hydrate was investigated. The compounds were tested for biological properties.     

Investigation of 7-((dioctylamino)methyl)quinoline-8-ol for uptake and removal of uranyl ions

A new 8-hydroxyquinoline derivative extractant was synthesized via the Mannich reaction from a secondary amine. Various analytical techniques (¹H, ¹³C NMR, FTIR, mass spectroscopy) were used to characterize our product. The use of this new extractant for the uptake and removal of uranyl ions in aqueous solution was investigated. Conditions for an effective sorption were optimized with respect to different experimental parameters in batch process. The results showed that the extraction rate increases for solutions with a pH in the range [0.65–1.13]. The total sorption capacity was 105 (mg g^?1) under optimum experimental conditions. The extraction of UO₂ ²⁺ was found to be quantitative (100 %) at initial uranyl concentration less than or equal to 41.59 mg/L. Thermodynamic parameters showed the adsorption of an endothermic process and a spontaneous nature, respectively.     

Structural and optical characterizations of rare earth pentaphosphates LnP5O14 (Ln = La, Gd) synthesized by the sol–gel process

The sol–gel chemistry route has successfully been used to prepare samples of LnP₅O₁₄ (Ln = La, Gd) pentaphosphates from lanthanides chlorides and phosphorous pentoxide dissolved in isopropanol. Crystallized powders of single phase were obtained after calcination of gels at 350 °C. The structural characterizations of materials were investigated by means of X-ray diffraction as well as infrared and Raman spectroscopies, whereas their thermal behavior has been studied by differential thermal analyse and thermogravimetric analyses. Powders morphology was analyzed by means of scanning electron microscopy and laser granulometry. The photoluminescence properties of the Eu³⁺ ions in sol–gel derived LaP₅O₁₄ and GdP₅O₁₄ samples were investigated and compared with homologous samples synthesized by the conventional solid state reaction.