Modification of Oligo- and Polylactides With Macrocyclic Fragments: Synthesis and Properties.

Products of lactic acid polycondensation (poly- and oligolactic acids) are widely used as packaging materials, drug delivery agents, implants etc. Variety of their applications is caused by a number of practically important properties, e.g., biocompatibility and biodegradability, non-toxicity, and mechanical durability. Modification of these polymers with different additives allows improving their properties and extending future applications. In this manner, stability toward degradation, recognition of some substrates, extended thermal stability etc. can be improved. Macrocyclic compounds are promising candidates as modifiers. They are able to provide polymer materials with additional binding sites, impart certain orientation to spatial arrangement of polymer chains, change hydrophilic-lipophilic balance, and redox properties. The latter one can be used for assembling various electrochemical sensors and biosensors that combine steric discrimination of the analytes caused by oligolactides and highly sensitive response to their quantities caused by redox labels introduced. Different composite materials based on oligolactides as matrices for such redox labels were described in the assemblies of biosensors for drugs, pesticides, and antioxidants detection. In this mini-review, methods for the synthesis of the lactic acid oligomers and those modified with the macrocyclic fragments (porphyrin, cyclodextrin, and cyclophane) have been described. The effects of modifiers on complexation, thermal, and aggregation properties of materials are described. Analytical performance of oligolactide based sensors and biosensors has been considered with particular emphasis to the mechanism of signal generation.

Phenyliminophenothiazine based self-organization of polyaniline nanowires and application as redox probe in electrochemical sensors.

Synthesis and application of nanostructured materials applicable in the assembly of electrochemical sensors is one of the important trends in material sciences and analytical chemistry. In this work, we have proposed and implemented simple non-template method for assembling nanofibers from the polyaniline ultrasonicated with phenyliminophenothiazine in aqueous media. Two-step procedure including association with emeraldine dispersion and reorganization under ultrasonication led to formation of nanofibrillar structures with average diameter of 20 nm. UV-spectroscopy confirms that association of phenyliminophenothiazine and polyaniline in acidic medium resulted in an intense absorption band at 900-910 nm due to donor-acceptor interaction between the reactants. The material combined emeraldine charge transmission with redox activity of phenyliminophenothiazine was found promising for electrochemical sensing. It was confirmed by comparison of characteristics of appropriate solid-contact sensors based on emeraldine and phenyliminophenothiazine toward Fe(III) ions, ascorbic acid and hydroquinone. In all the cases, the use of phenyliminophenothiazine results in a wider concentration range and more reproducible signal against characteristics of similar sensor based on polyaniline. The applicability of the sensor was confirmed by determination of iron content in commercial medication.