DNA Modified with Boron–Metal Cluster Complexes [M(C2B9H11)2]—Synthesis, Properties, and Applications

Abstract

Together with tremendous progress in biotechnology, nucleic acids, while retaining their status as “molecules of life”, are becoming “molecular wires”, materials for the construction of molecular structures at the junction between the biological and abiotic worlds. Herein, we present an overview of the approaches for incorporating metal centers into nucleic acids based on metal–boron cluster complexes (metallacarboranes) as the metal carriers. The methods are modular and versatile, allowing practical access to innovative metal-containing DNA for various applications, such as nucleic acid therapeutics, electrochemical biosensors, infrared-sensitive probes, and building blocks for nanoconstruction.

Synthesis and study ofC-substituted methylthio derivatives of cobalt bis(dicarbollide)

“…[1][2][3][4][5] Among the various derivatives of carboranes, special attention is paid to p-complexes of transition metals with carborane ligands, called metallacarboranes. The most known of them, cobalt bis(dicarbollide) [3,3 0 -Co(1,2-C 2 B 9 H 11 ) 2 ] À attracts increasing interest from researchers working in various elds from medical chemistry to [6][7][8][9][10][11] materials science [12][13][14][15][16][17][18] to due to its extraordinary high stability, low toxicity 19 and almost unlimited possibilities for chemical modication. 20,21 Recently, we suggested that cobalt bis(dicarbollide) can be used as a structural element in the design of molecular switches.…”

Novel Convenient Approach to the Solid-Phase Synthesis of Oligonucleotide Conjugates

“…The incorporation of boron clusters into nucleic acids appears promising for the creation of new boron delivery agents for boron neutron capture therapy (BNCT) capable of specific interaction with nucleic acids inside the cells [42]. Several methods were developed for modification of oligonucleotides with boron clusters attached to internal positions of an oligonucleotide chain, such as sugar residues, nucleobases, or phosphorus atoms of the internucleotide linkages [14,43]. The reported methods for the synthesis of oligonucleotides modified with borane clusters include a post-synthetic “click”-chemistry approach based on Huisgen 1,3-dipolar cycloaddition (see, e.g., [44]) and an H-phosphonate or phosphoramidite solid-phase approach using modified nucleotide monomers (see, e.g., [45]).…”

“…The oligonucleotide conjugates attract particular attention as therapeutics for the treatment of cancer, genetic and viral diseases, and as imaging and diagnostic tools in biomedicine (see, e.g., [1,2,3,4,5,6,7,8,9,10,11,12]). They also find broad application in other fields such as the development of biohybrid nanomaterials and agents for biocatalysis, design of biomimetics, template-directed biosynthetic chemistry, magnetic and (opto)-electronic nanomaterial design (see, e.g., [13,14,15]). Taking into account the vast diversity of ligands and research tasks, the development of convenient and efficient approaches to the synthesis of oligonucleotide conjugates remains a significant challenge.…”

Terminal Mono- and Bis-Conjugates of Oligonucleotides with Closo-Dodecaborate: Synthesis and Physico-Chemical Properties

“…The most common methods of incorporating boron clusters to the oligonucleotides rely on modifications of ribose 2'-position or heterocyclic bases, using pre-synthetic or post-synthetic techniques [1,8,9]. So far, only one study has been published on the terminal oligonucleotide modifications by the boron clusters [10].…”