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).     

Die Reaktion von Tellurhexafluorid mit Trimethylamin,Strukturen der TeF5−- und SeF5−-Anionen

Reaction of Telluriumhexafluoride and Trimethylamine, Structures of the TeF₅^? and SeF₅^? Anions The reaction of TeF₆ and (CH₃)₃N is of the redox kind, resulting in reduction of tellurium: X-ray single crystal analysis reveals the compounds (CH₃)₂N? CH₂? N(CH₃)₂⁺TeF₅^? and [(CH₃)₃NH⁺]₅(TeF₅^?)₃(HF₂^?)₂. By comparison with published data it can be shown that this mixture is identical to previously published [(CH₃)₃N]₂TeF₆. The latter was supposed to be one of the few examples of tellurium in a coordination state of eight. (CH₃)₄N⁺TeF₅^? and (CH₃)₄N⁴SeF₅^? are obtained and their structure is investigated by single crystal x-ray methods also. The anions SF₅^?, SeF₅^? and TeF₅^? are discussed in terms of weak interactions.     

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.     

Health-based pharmaceutical pay-for-performance risk-sharing agreements

Many new drugs, such as biologics and cancer drugs, are very costly. However, their effectiveness outside of clinical trial settings is often uncertain at the time they gain market approval. This uncertainty may reflect a lack of real-world outcomes data, as opposed to clinical trials data, for a typical patient population. A risk-sharing agreement is a contract between a drug manufacturer and a healthcare payer to help manage uncertainties regarding the cost and effectiveness of those drugs. In this paper, we model a risk-sharing agreement in which a proportion of total sales is rebated. We model disease progression using a continuous time Markov chain with uncertain transition rates. We examine the performance of this risk-sharing agreement from the manufacturer’s perspective and investigate the conditions under which the manufacturer will make a profit. We illustrate with a numerical model parameterized using data from a Phase 2 clinical trial of an oncology drug that was subjected to a risk-sharing agreement in the UK.     

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.     

Silica-coated MgAl2O4 nanoparticles supported phosphotungstic acid as an effective catalyst for synthesis of α-aminophosphonates

Research on Chemical Intermediates - In this research, a recoverable catalyst (MgAl2O4@SiO2–PTA) was prepared by a simple utilization method. The prepared catalyst was characterized by XRD,...     

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.