Biological membranes, in addition to being a cell boundary, can host a variety of proteins that are involved in different biological functions, including selective nutrient transport, signal transduction, inter- and intra-cellular communication, and cell-cell recognition. Due to their extreme complexity, there has been an increasing interest in developing model membrane systems of controlled properties based on combinations of polymers and different biomacromolecules, i.e., polymer-based hybrid films. In this review, we have highlighted recent advances in the development and applications of hybrid biomimetic planar systems based on different polymeric species. We have focused in particular on hybrid films based on (i) polyelectrolytes, (ii) polymer brushes, as well as (iii) tethers and cushions formed from synthetic polymers, and (iv) block copolymers and their combinations with biomacromolecules, such as lipids, proteins, enzymes, biopolymers, and chosen nanoparticles. In this respect, multiple approaches to the synthesis, characterization, and processing of such hybrid films have been presented. The review has further exemplified their bioengineering, biomedical, and environmental applications, in dependence on the composition and properties of the respective hybrids. We believed that this comprehensive review would be of interest to both the specialists in the field of biomimicry as well as persons entering the field.

Macromolecules with well-defined structures in terms of molar mass and monomer sequence became interesting building blocks for modern materials. The precision of the macromolecular structure makes fine-tuning of the properties of resulting materials possible. Conjugated macromolecules exhibit excellent optoelectronic properties that make them exceptional candidates for sensor construction. The importance of chain length and monomer sequence is particularly important in conjugated systems. The oligomer length, monomer sequence, and structural modification often influence the energy bang gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecules that reflect in their properties. Moreover, the supramolecular aggregation that is often observed in oligo-conjugated systems is usually strongly affected by even minor structural changes that are used for sensor designs. This review discusses the examples of well-defined conjugated macromolecules based on oligo(arylene ethynylene) skeleton used for sensor applications. Here, exclusively examples of uniform macromolecules are summarized. The sensing mechanisms and importance of uniformity of structure are deliberated.

Electrochemically triggered self-assembly can be effectively utilized to produce electroactive materials of tailored properties for various applications, such as sensor development. Here, we present a thin sensor film based on tannic acid (TA) and silver nanoparticles (AgNPs), ionically imprinted via electrodeposition and tailor-designed for electrochemical tracing of aluminum ions, Al(III). In the first stage, the conditions for the Al(III) printing of TA films onto an indium-tin-oxide (ITO) electrode via electrodeposition are established and optimized. To form an AgNPs-containing film, AgNPs are presynthesized via a direct reduction of Ag(I) by TA resulting in TA-stabilized AgNPs ([email protected]) of 1–4 nm in size, as observed by dynamic light scattering. Next, Al(III) ions are added to complex the TA molecules adsorbed on the surface of AgNPs. The resulting Al(III)/[email protected] mixture is then electrodeposited onto the ITO surface by applying an anodic potential to form a film. As a result, a mesh-structured layer composed of AgNPs with TA on their surface and electrochemically cross-linked via TA–TA covalent bonds at the Al(III)-free coordination sites is formed. The introduction of Al(III) ions bonded via coordination bonds with TA and their consecutive removal using sodium fluoride formed vacancies ready to bind Al(III) ions from the analyzed solution allowing their electrochemical sensing, as monitored by cyclic voltammetry, quartz crystal microbalance, and X-ray photoelectron spectroscopy. The film was employed for sensing of neurotoxic Al(III) in human serum. A linear correlation between the current value at 0.9 V and the concentration of Al(III) was obtained in the range between 0.10 and 0.298 μM.

Macromolecules with well-defined structures in terms of molar mass and monomer sequence became interesting building blocks for modern materials. The precision of the macromolecular structure makes fine-tuning of the properties of resulting materials possible. Conjugated macromolecules exhibit excellent optoelectronic properties that make them exceptional candidates for sensors construction. The importance of chain length and monomer sequence is particularly important in conjugated systems. The sequence lengths, monomer sequence and structural modification often influence the energy bang gap between HOMO and LUMO orbitals of the molecules that reflect in their properties. Moreover, the supramolecular aggregation that is often observed in oligo-conjugated systems is usually strongly affected by even minor structural changes that are used for sensor designs. This review summarizes the examples of well-defined conjugated macromolecules based on oligo(arylene ethynylene)s skeleton used for sensor applications. The sensing mechanisms and importance of uniformity of structure are discussed.

Supramolecular metal-polyphenolic thin sensor films represent a unique class of composite materials. Their properties and sensitivity can be easily modified via controlled self-assembly of their molecular components. Among the different assembly methods, electrochemically triggered processes are extremely powerful because they allow spatial confinement of the film buildup via an electrical stimuli-controlled process. In this article, an approach to employ the electrochemically assisted self-assembly of a multicomponent supramolecular film based on a naturally occurring polyphenol, tannic acid (TA), is featured. Here, the capacity of polyphenolic compounds to form complexes with metal ions, as well as to act both as reducing agents and stabilizers in colloidal synthesis of metal nanoparticles (NPs) is utilized. The electrochemically triggered self-assembly can be coupled with the ion – printing method, in which the targeted metal ion, in this case Al(III), is incorporated into the film during the synthesis and chemically removed afterwards. This procedure results in a template-like structure of the film with openings ready to bind the same metal ion from the probed solution, thus significantly improving the selectivity of the sensor formed and enhancing its applicability for sensing of toxic metal ions in complex aqueous solutions, such as physiological fluids.