Solid Contact Potentiometric Sensors Based on a New Class of Ionic Liquids on Thiacalixarene Platform

New solid-contact potentiometric sensors have been developed for hydrogen phosphate recognition on the basis of ionic liquids containing tetrasubstituted derivatives of thiacalix[4]arene in cone and 1,3-alternate conformations with trimethyl- and triethylammonium fragments at the lower rim substituents. The recognition of selected anions including carbonate, hydrogen phosphate, perchlorate, oxalate, picrate, and EDTA was conducted using electrochemical impedance spectroscopy with ferricyanide redox probe. For the potentiometric sensor assembling, the ionic liquids were stabilized by multiwalled carbon nanotubes and carbon black deposited on the glassy carbon electrode. The influence of support, steric factors and modification conditions on the sensor performance has been investigated. As was shown, potentiometric sensors developed make it possible to selectively determine hydrogen phosphate anion within the concentration range from 1 × 10−2 to 1 × 10−6 M and limit of detection of 2 × 10−7−1 × 10−6 M with unbiased selectivity coefficients varied from 1.2 × 10−1 to 1.0 × 10−8 (carbonate, acetate, oxalate, succinate, glutharate, glycolate, and malonate anions)

Editorial of Special Issue “Functional Nanomaterials Based on Self-Assembly”

In recent years, the design and creation of new functional nanosystems and nanomaterials similar in their properties to biological systems showed remarkable progress as an interdisciplinary field of research combining chemistry, biology, and physics [...

Design of Micro- and Nanoparticles: Self-Assembly and Application

The modern world throws down an increasing number of challenges to humanity [...

The Role of Calix[n]arenes and Pillar[n]arenes in the Design of Silver Nanoparticles: Self-Assembly and Application

Silver nanoparticles (AgNPs) are an attractive alternative to plasmonic gold nanoparticles. The relative cheapness and redox stability determine the growing interest of researchers in obtaining selective plasmonic and electrochemical (bio)sensors based on silver nanoparticles. The controlled synthesis of metal nanoparticles of a defined morphology is a nontrivial task, important for such fields as biochemistry, catalysis, biosensors and microelectronics. Cyclophanes are well known for their great receptor properties and are of particular interest in the creation of metal nanoparticles due to a variety of cyclophane 3D structures and unique redox abilities. Silver ion-based supramolecular assemblies are attractive due to the possibility of reduction by “soft” reducing agents as well as being accessible precursors for silver nanoparticles of predefined morphology, which are promising for implementation in plasmonic sensors. For this purpose, the chemistry of cyclophanes offers a whole arsenal of approaches: exocyclic ion coordination, association, stabilization of the growth centers of metal nanoparticles, as well as in reduction of silver ions. Thus, this review presents the recent advances in the synthesis and stabilization of Ag (0) nanoparticles based on self-assembly of associates with Ag (I) ions with the participation of bulk platforms of cyclophanes (resorcin[4]arenes, (thia)calix[n]arenes, pillar[n]arenes)

Synthesis of Water-Soluble Amino Functionalized Multithiacalix[4]arene via Quaternization of Tertiary Amino Groups

A convenient approach to the synthesis of multithiacalix[4]arene derivatives containing amino groups and phthalimide fragments by the formation of quaternary ammonium salts is presented. As the initial macrocycle for the synthesis of multithiacalix[4]arenes, a differently substituted p-tert-butylthiacalix[4]arene containing bromoacetamide and three phthalimide fragments was used in a 1,3-alternate conformation. The macrocycle in cone conformation containing the tertiary amino groups was found to be a convenient core for the multithiacalix[4]arene systems. Interaction of the core multithiacalix[4]arene with monobromoacetamide derivatives of p-tert-butylthiacalix[4]arene resulted in formation in high yields of pentakisthiacalix[4]arene containing quaternary ammonium and phthalimide fragments. The removal of phthalimide groups led to the formation of amino multithiacalix[4]arene in a good yield. Based on dynamic light scattering, it was shown that the synthesized amino multithiacalix[4]arene, with pronounced hydrophobic and hydrophilic fragments, formed dendrimer-like nanoparticles in water via direct supramolecular self-assembly

PAMAM-calix-dendrimers: Synthesis and Thiacalixarene Conformation Effect on DNA Binding

A convenient method for the synthesis of the first generation PAMAM dendrimers based on the thiacalix[4]arene has been developed for the first time. Three new PAMAM-calix-dendrimers with the macrocyclic core in cone, partial cone, and 1,3-alternate conformations were obtained with high yields. The interaction of the obtained compounds with salmon sperm DNA resulted in the formation of the associates of the size up to 200 nm, as shown by the UV-Vis spectroscopy, DLS, and TEM. It was demonstrated by the CD method that the structure of the DNA did not undergo significant changes upon binding. The PAMAM-calix-dendrimer based on the macrocycle in cone conformation stabilized DNA and prevented its degradation

Macrocyclic Ionic Liquids with Amino Acid Residues: Synthesis and Influence of Thiacalix[4]arene Conformation on Thermal Stability

Novel thiacalix[4]arene based ammonium ionic liquids (ILs) containing amino acid residues (glycine and L-phenylalanine) in cone, partial cone, and 1,3-alternate conformations were synthesized by alkylation of macrocyclic tertiary amines with N-bromoacetyl-amino acids ethyl ester followed by replacing bromide anions with bis(trifluoromethylsulfonyl)imide ions. The melting temperature of the obtained ILs was found in the range of 50–75 °C. The effect of macrocyclic core conformation on the synthesized ILs’ melting points was shown, i.e., the ILs in partial cone conformation have the lowest melting points. Thermal stability of the obtained macrocyclic ILs was determined via thermogravimetry and differential scanning calorimetry. The onset of decomposition of the synthesized compounds was established at 305–327 °C. The compounds with L-phenylalanine residues are less thermally stable by 3–19 °C than the same glycine-containing derivatives