Anion Recognition by Urea Derivatives of Anthraquinone: Dihydrogen Phosphate Ion Selective Neutral Receptors

Three urea derivatives of anthraquinone were synthesized and they showed a high selectivity for dihydrogen phosphate ions.     

REACTION DES O,O-DIETHYL OXO-1 ALKANEPHOSPHONATES AVEC LES DERIVES DE L'HYDRAZINE: UNE VOIE DE SYNTHESE DES HYDRAZONES α-PHOSPHONATEES ET DES HYDRAZIDES

Abstract

Under the normal conditions, the reaction of hydrazine and methylhydrazine with OO-diethyl 1 oxoalkane phosphonates 1 proceeds by cleavage of the phosphorus-carbon bond and leads to the formation of diethylphosphite 2 and N-acylhydrazide 3 . A procedure has been developed for the synthesis of new primary hydrazone of OO-diethyl 1-oxoalkane phosphonates 4 . A mechanism is proposed. The structure of those compounds 4 was confirmed by NMR and IR spectroscopy.     

Cl3CCONH2/PPh3: A Versatile Reagent for Synthesis of Esters

Cl₃CCONH₂/PPh₃ was a versatile reagent to convert carboxylic acids into their corresponding acid chlorides. This intermediate was clearly confirmed by spectroscopic methods (IR, ¹H, ¹³C NMR). This one-pot reaction of in situ acid chloride generated with various alcohols successfully furnished the corresponding esters in moderate to excellent yields.     

Preparation and characterization of novel polyimide‐silica hybrids

Polyimide‐silica (PI‐SiO₂) hybrids were prepared from a novel polyimide (PI), derived from pyromellitic dianhydride (PMDA), 1,6‐bis(4‐aminophenoxy)hexane (synthesized) and 4,4′‐oxydianiline. SiO₂ networks (5–30 wt%) were generated through sol–gel process using either tetraethylorthosilicate (TEOS) or a mixture of 3‐aminopropyltriethoxysilane‐PMDA‐based coupling oligomers (APA) and TEOS. Thin, free standing hybrid films were obtained from the respective mixtures by casting and curing processes. The hybrid films were characterized using Fourier transform infrared, ²⁹Si nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectrometry and atomic force microscopy (AFM) techniques. ²⁹Si NMR results provide information about formation of organically modified silicate structures that were further substantiated by FE‐SEM and AFM micrographs. Contact angle measurements and thermogravimetric thermograms reveal that the addition of APA profoundly influences surface energy, interfacial tension, thermal stability and the residual char yield of modified hybrids in comparison to those obtained by mixing only TEOS. It was found that reduced particle size, efficient dispersion and improved interphase interactions were responsible for the eventual property enhancement. Copyright © 2012 John Wiley & Sons, Ltd.     

Monitoring the status of T-cell activation in a microfluidic system

Leukocyte adhesion to the endothelium through surface molecules such as E-selectin and intercellular adhesion molecule-1 (ICAM-1) is a critical cellular event reflecting the physiological status of both cell types. Here we present a microfluidic system that can not only easily monitor the interaction between leukocytes and endothelial cells under physiological conditions, but also screen drug candidates for potential modulation of this interaction. Shear stress, which is an important factor for the binding of activated T cells to tumor necrosis factor-alpha (TNF-α)-treated human umbilical vein endothelial cells (HUVECs), was easily controlled by adjusting the flow rate in the microfluidic system. Whole blood of patients with systemic lupus erythematosus (SLE) who have auto-reactive T cells were infused into the activated HUVECs which subsequently showed a higher level of binding compared to a control blood sample from a person without SLE. When these autoreactive T cells were treated with immunosuppressors tacrolimus and cyclosporin A, the binding of the T cells to HUVECs was dramatically decreased. Therefore, this microfluidic system is capable of differentiating the physiological status of T cells or endothelial cells representing different disease conditions, as well as being useful for the identification of novel reagents that modulate the functions of leukocytes or endothelial cells.     

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.     

Heats of adsorption using temperature programmed adsorption equilibrium: application to the adsorption of CO on Cu/A12O3 and H2 on Pt/Al2O3

A new simple analytical procedure is described that allows the determination of the heats of adsorption (denoted E(theta)) of adsorbed species at several coverages (theta's) using a single experiment. This procedure is an extension of an original method previously developed (denoted AEIR: adsorption equilibrium infrared spectroscopy). A mass spectrometer is used to determine the amounts of gas (in the present study, CO and H2) either desorbed from or adsorbed on a metal supported catalyst (4.7% Cu/Al2O3 and 2.9% Pt/Al2O3) during the perturbation of the adsorption equilibrium due to a controlled change of the adsorption temperature (Ta) at a quasi-constant adsorption pressure (Pa). These amounts allow us to follow the evolution of the adsorption equilibrium coverage (theta(e)) with Ta at the quasi-constant partial pressure (Pa). Then, the curve theta(e) = f(Ta) provides Etheta = f(theta) with the support of an adsorption model. This procedure presents several advantages as compared to the TPD methods, in particular, considering the theoretical supports linked to the exploitation of the experimental data. As compared to AEIR, the TPAE procedure allows one to study the heats of adsorption of adsorbed species that are not detectable by IR. However, it is not adapted if surface reactions occur in parallel to adsorption/desorption processes.