Reactions of α-Hydroxyphosphonates under PTC Conditions

Abstract

We found, that dialkyl phosphite 1 and oxo-compound 2 in an equilibrium reaction give an adduct α-hydroxyphosphonate 5 un -der phase-transfer catalytic conditions [K₂CO₃/TEBA/dichloroethane or aromatic solvents (solid-liquid PTC); 50% NaOH/TEBA/dichloroethane or benzene (liquid-liquid PTC)]. On the other hand 3, is transformed to phosphate 4 or to α-alkoxyphosphonate 5 in the presence of alkylating agent using PTC circumstances.     

Influence of dissolution processing of PVA blends on the characteristics of their hydrogels synthesized by radiation—Part I: Gel fraction,swelling, and mechanical properties

In this work several hydrogels were obtained with two different poly(vinyl alcohol)s/PVAs as the main polymer in aqueous solutions containing 10% of PVA, 0.6% of agar, and 0.6% of κ-carrageenan (KC), cross-linked by gamma-rays from a ⁶⁰Co irradiation source. The PVAs tested have different degrees of hydrolysis and viscosities at 4% with values closed to 30 mPa s. The aqueous polymeric solutions were prepared using two distinct processes: the simple process of heating–stirring and that of making use of an autoclave. The purpose of this study was to evaluate the influence of the dissolution process by means of both methods on the hydrogels’ properties obtained. These were investigated by means of degree of cross-linking/gel fraction, degree of swelling in water, and some mechanical properties. The results that are obtained for hydrogels synthesized from solutions of PVA, agar, KC, and blends thereof prepared by both dissolution processes showed higher degrees of swelling for hydrogels from the autoclaved polymer solutions than those from the solutions prepared by simple heating–stirring process. Furthermore, their hydrogels containing totally hydrolyzed PVA displayed higher tensile strength and lower elongation properties.     

Helicenophyrins: Expanded Carbaporphyrins Incorporating Aza[5]helicene and Heptacyclic S‐Shaped Aza[5]helicene Motifs

Incorporation of phenanthrene into a hexaphyrin(1.1.1.1.1.0) frame resulted in intramolecular ring fusion, thus giving rise to chiral helicenophyrins. These molecules contain helicene and porphyrin features by incorporating either an aza[5]helicene or heptacyclic S‐shaped aza[5]helicene.     

2-Morpholinoethyl-substituted <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene (NHC) precursors and their silver(I)NHC complexes: synthesis,crystal structure and in vitro anticancer properties

In this study, a series of unsymmetrically 2-morpholinoethyl-substituted benzimidazolium salts and their Ag(I)NHC complexes were synthesized. The 1,3-dialkylbenzimidazolium salts (1a–d) were synthesized in dimethylformamide at 80 °C temperature from the N-(2-morpholinoethyl)benzimidazole and alkyl halides. The Ag(I)NHC complexes (2a–d) were synthesized in dichloromethane at room temperature from the benzimidazolium salts and Ag₂O. All compounds were characterized by spectroscopic techniques (NMR and FT-IR) and elemental analyses. Also, the salt 1c and complex 2c were characterized by single-crystal X-ray crystallography. Anticancer activities of 2-morpholinoethyl-substituted benzimidazolium salts and Ag(I)NHC complexes were investigated against the MCF-7 breast cancer cell line, and the IC₃₀ and IC₅₀ values of these compounds were found to be in the range of 241–490 and 6–14 µM, respectively.     

Polymer microfluidic chips for electrochemical and biochemical analyses

Our recent developments concerning the fabrication of polymer microchips and their applications for biochemical analyses are reviewed. We first describe two methods of fabrication of polymer microfluidic chips, namely UV-laser photoablation and plasma etching that are well suited for the prototyping and mass fabrication of microchannel networks with integrated microelectrodes. These microanalytical systems can be coupled with various detection means including mass spectrometry, and their applications in capillary electrophoresis are presented here. We also present how UV laser photoablation can be used for the patterning of biomolecules on polymer surfaces for generating two-dimensional arrays of microspots to carry out affinity assays. Finally, the use of the microchips for the development of fast affinity and immunological assays with electrochemical detection is presented, demonstrating the potential of these polymer microchips for medical diagnostics and drug discovery.     

Gas chromatography-mass spectrometry as a tool for estimating odour concentrations of biofilter effluents at aerobic composting and rendering plants

The relationship between chemical concentrations (gas chromatography–mass spectrometry analysis) and odour concentrations (olfactometry) was studied for biofilter emissions from four aerobic vegetable, fruit and garden waste (VFG) composting plants and one animal rendering plant. For the VFG composting plants, the study revealed a good linear relationship of the odour concentration with the total volatile organic compounds (VOC) concentration (R²=0.97, n=16) as well as with the concentration of esters and ketones (R²=0.9, n=19). For biofilter emissions of the animal rendering plant, the total VOC concentration was a poor estimator for odour concentration. However, for this type of odour, concentrations of organic sulphur containing compounds correlated well with odour concentrations (R²=0.94, n=8). The results of the study also showed that the relationship between chemical and odour concentrations is specific for each type of odour and cannot be generalized.