Supramolecular associates of double-decker lanthanide phthalocyanines with macromolecular structures and nanoparticles as the basis of biosensor devices

Abstract

The electronic spectroscopy technique is used to study the properties of solutions of double decker diphthalocyanine complexes of lanthanides LnPc 2 (Ln = Ho, Er, Yb, Lu) in chloroform, dimethyl formamide, water-micellar systems, solutions of proteins, and polymers, as well as on the surface of silica nanoparticles. In all the studied systems, a correlation is established between the positions of maxima of absorption bands of LnPc 2 and the ionic radius of the complexing metal. Redox processes determined by the nature of the solubilizer are detected in supramolecular associates of LnPc 2 with macrocompounds and nano particles. Finally, prototypes of sensor systems are suggested for determination of albumin and silica nano particles in solutions. Films of polyvinyl pyrrolidone and polyvinyl alcohol containing LuPc 2 and YbPc 2 are obtained, for which sensor response to albumin and nanosilica is also established. On the whole, the results show good prospects for development of sensor devices based on the studied systems.

Evaluation and Characterization of Ultrathin Poly(3-hydroxybutyrate) Fibers Loaded with Tetraphenylporphyrin and Its Complexes with Fe(III) and Sn(IV)

“…Along with the bactericide activity, due to the specific geometry and electronic structure, the complexes of metals with porphyrins have a significant effect on the crystallization and segmental orientation of macromolecules [ 22 ]. The pristine porphyrin molecules as well as their metal complexes are amphiphilic [ 23 ] or even hydrophobic [ 24 ] that promote their aggregation in the form of nanoparticles [ 23 , 25 , 26 , 27 ]. Depending on the nature of the metal included in metalloporphyrins, they exhibit a variable tendency to aggregation [ 28 ] that determines their ability to act as nucleating agents during polymer crystallization.…”

Synthesis, Spectroscopic Properties and Redox Behavior Kinetics of Rare-Earth Bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato Metal Complexes with Er, Lu and Yb

“…Due to the possibility of accepting or transferring an electron, various redox forms can exist in solution: anionic “blue” [(Pc 2− ) 2 Ln 3+ ] − and cationic “red” [(Pc – ) 2 Ln 3+ ] + ones [ 29 ]. It should be noted that there are few data in the literature on kinetically controlled redox reactions involving diphthalocyanines [ 30 , 31 ]. Further, the kinetic behavior for cyano-substituted sandwich phthalocyanines is considered depending on the nature of the lanthanide ion.…”

Lanthanide–tetrapyrrole complexes: synthesis, redox chemistry, photophysical properties, and photonic applications

“…More recently, a new prototype of an albumin and nanosilica sensing system was proposed based on supramolecular films of polyvinyl pyrrolidone and polyvinyl alcohol comprising Lu III /Yb III diphthalocyanine double-decker complexes, highlighting the biomedical sensing potential of lanthanide sandwich complexes protected in biocompatible multicomponent host systems. 353 In 2019, Nyokong's group reported new electrochemical sensors for detecting 4-chlorophenol, a toxic organic contaminant, in aqueous media by modifying a glassy carbon electrode (GCE) with two forms of blue and green diethylaminophenoxy-bearing thulium double-decker phthalocyaninates, capitalizing on their respective electrocatalytic effect arising predominantly from the redox cycles of the Pc rings. The blue form stands for [(Pc 2À )Tm III (Pc 2À )] À (i.e., both the HOMO and LUMO are fully filled), with its overall charge compensated by a hexadecyltrimethylammonium cation, and responds better to oxidizing analytes, while the green form [(Pc À1 )Tm III (Pc 2À )] with one electron hole prefers reducing analytes.…”