Supermolecular Nanoentities of Vitamin B₁₂ Derivative as a Link in the Evolution of the Parent Molecules During Self-Assembly at the Air–Water Interface

Abstract

Nanoarchitectures with promising properties have now been formed from many important biomolecules. However, the preparation of nanoparticles of vitamin B 12 and its derivatives remains an ongoing research challenge. This paper describes the formation of supermolecular nanoentities (SMEs) of vitamin B 12 derivatives, unique nanoparticles with strong noncovalent intermolecular interactions, emerging properties, and activity. These were created by a nanoarchitectonic approach using directed assembly of layers at the air−water interface as a link in the chain of evolution of the parent molecules under specially created conditions. Such layers can be represented as a nanocosm, where, at a critical density, the assemblies act as nanoreactors in which the transformation of the original material occurs. The discovered SMEs not only replicate the functioning of vitamin B 12 assemblies with proteins in living organisms and act as vitamin B 12 -depended enzymes but also demonstrate important advantages over vitamin B 12 . They are more efficient in oxygen reduction/evolution reactions and in transformation into other forms. These SMEs, in performing advanced tasks, are an alternative to widely used materials based on noble metals for catalysis, medicine, and environment protection. Our findings open new perspectives both for the fabrication of novel SMEs of biomolecules and for a better understanding of the evolution of biomolecules in nature.

High Reactivity of Supermolecular Nanoentities of a Vitamin B12 Derivative in Langmuir–Schaefer Films Toward Gaseous Toxins

“…The structure of the floating monolayers at low surface pressures (less than 3 mN/m) was analyzed within the framework of an original model and method for the quantitative analysis of compression isotherms of nanostructured M-monolayers. Details can be found in the Supporting Information (Supporting Note 7) and in our previous works. , The data were analyzed by using Origin version 7.5.…”

“…For calculations of floating layer characteristics, the following geometric parameters of the molecules were used: linear dimensions (sides are equal to 2.2 3.2, and 1.1 nm); projection areas in a free state A proj‑face 5 nm 2 and A proj‑edge 2.1 nm 2 and areas in a packed state A pack‑face around 6 nm 2 . When calculating the monolayer state on water, the area of the circumscribed rectangle (3.5 nm 2 ), or, in polylayers, the area of the densest packing (2.5 nm 2 ) was taken as the value of A pack‑edge …”

“…When calculating the monolayer state on water, the area of the circumscribed rectangle (3.5 nm 2 ), or, in polylayers, the area of the densest packing (2.5 nm 2 ) was taken as the value of A pack-edge . 56 UV−Vis Spectroscopy Measurements. UV−vis spectra were recorded on a Shimadzu UV-1800 UV−vis spectrophotometer in sealed quartz cells (1.3 mL) at 25 °C.…”

“…Nowadays, nanostructures of numerous biomolecules having different properties from those of the parent molecules and with great potential for various applications have been reported. , Self-assembly is a key player in material nanoarchitectonics, − the nanostructures formed in this way arising from molecules carrying side groups that promote the process. Supramolecular polymers have been created using diverse self-assembly strategies. , The formation of different kinds of molecular assemblies from precursor compounds at the water surface has been reported. , We previously demonstrated the possibility of supramolecular design at the air–water interface by controlling the self-assembly of tetrapyrrole compounds into 2D and 3D nanostructures. − The concept of nanostructuring of organic compounds at the air–water interface and a model of a floating layer, the structural units of which can be both individual molecules (Langmuir’s approach, special case) and their major nanostructures (so-called M-nanostructures, general case), were presented. − The formation of the porphyrin supermolecules from magnesium porphine, a functional element of chlorophyll, was reported …”

“…Recently, we reported the formation of the first supermolecular nanoentities (SMEs) of a vitamin B 12 derivative (monocyano-species of heptabutyl cobyrinate), unique nanoparticles with strong noncovalent intermolecular interactions, and emerging optical and redox properties. 56 These were created from the dicyano-form of heptabutyl cobyrinate by a nanoarchitectonic approach using directed assembly of layers at the air−water interface as a link in the chain of evolution of the parent molecules under specially created conditions. Such layers can be represented as a nanocosm, where at a critical density, the assemblies act as nanoreactors in which the transformation of the original material occurs.…”