Ten Ag + -selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with π-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag + sensors can be maintained in the subnanomolar range for at least one month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3× 10 −11 M (potentiometrically) and 2 × 10 −11 M Ag + (optically) are found with bridged thiacalixarenes.
The synthesis of pamidronic acid and sodium pamidronate dihydrate from β‐alanine and P‐reagents (phosphorus trichloride and phosphorous acid) was investigated at 75°C in different solvents, and the preparation was optimized. In sulfolane, the use of 2 equiv of phosphorus trichloride and phosphorous acid was found the optimum to lead to pamidronic acid in a yield of 63%. In methanesulfonic acid, 3.2 equiv of phosphorus trichloride was necessary without any phosphorous acid to give pamidronate dihydrate in the best yield (57%) after hydrolysis and pH adjustment. In the first case, the P‐nucleophile may be (HO)2P–O–PCl–O–P(OH)2 or (HO)2P–O–PCl2, whereas in the second case, the P‐reactant is probable Cl2P–O–S(O)2Me. It can be said that the mechanism proposed for the formation of pamidronic acid is highly influenced by the solvent used, as it determines the necessary P‐reagent(s). Our results promote the “on purpose” planning of the synthesis of dronates.
We report on the synthesis and trace analytical application of ionophore-gold nanoparticle conjugates as a basis of a new concept in confining ionophores to ion-selective membranes using inert nanoparticle carriers.
A series of substituted diethyl arylphosphonates was synthesized by the microwave‐assisted Arbuzov reaction of triethyl phosphite and aryl bromides in the presence of NiCl2 as the catalyst under solvent‐free conditions in good yields. The resulting phosphonates were hydrolyzed to the corresponding arylphosphonic acids whose acidity was evaluated by physicochemical methods.
The chiral monoaza-15-crown-5 lariat ether annelated to methyl-4,6-O-benzylidene-α-D-glucopyranoside has been applied as a phase-transfer catalyst in several Michael addition reactions under mild conditions affording the adducts with good to excellent enantioselectivities. In the addition of α-substituted diethyl malonates to trans-chalcones, the substituents of the reactants had a significant impact on the yield and enantioselectivity. Among the reactions of substituted diethyl malonates, that of diethyl-2-acetoxymalonate gave the best results (up to 97% ee). New phase-transfer-catalyzed cyclopropanation reactions (MIRC reactions) of a few enones were also developed using diethyl 2-bromomalonate as the nucleophile. The corresponding chiral cyclopropane derivatives were formed with enantioselectivities up to 92% from 2-benzylidenemalononitrile starting materials, in up to 60% enantiomeric excess using 2-benzylidene-1,3-diphenyl-1,3-propanediones, and in up to 88% optical purity applying trans-chalcones as the starting materials.
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