Modern chemistry with refined orthogonal conjugations and highly sensitive, high resolution analytics in vitro and in vivo, facilitates development of advanced systems for biomedical application such as hybrid smart materials. These materials have the advantages of addressing multiple functions in a single tool: the system can be at the same time a drug carrier or/and have pharmacological activity itself, a diagnostic agent as well as a synergistic physical therapy element (neutron capture element, magnetic targeting and hyperthermia agent, IR sensitive element, etc.). The employement of biocompatible, nanosized scaffolds with well defined properties in terms of size, composition and surface characteristics is a priority in this field. As result of research of the last decades in the field of polyhedral boron clusters (boranes, carboranes and metallacarboranes), promising materials with unique features emerged [1]. Oligofunctionalization of boron clusters with more than one substituent (R) is of fundamental importance. The substituents R, that may be identical or differ from each other in a predetermined manner can further be used as spacer for initiation points of polymerization processes to obtain attractive molecular modules for nanoconstruction by selfassembly or to form compact, rigid, and densely populated surface-functionalized biomimetic nanosystems. Functionalization of the three vertices of o-carborane and polymerization of DNA from the surface of the obtained tripod, anchored to a solid support, have been previously reported by our group [2]. This work is now extended to the functionalization of novel oligopods of cobalt bis(1,2-dicarbollide) anion [Co(C2B9H11)2 −] and closo-dodecaborate dianion [B12H12 2−] (FIGURE 1). In the former case two approaches are tested: 1) direct functionalization of dihydroxy cobalt bis(1,2-dicarbollide) anion [3] and 2) partial degradation of functionalized at position 9 ortho-carborane followed by its reaction with cobalt salt to obtain cobalt bis(1,2- dicarbollide) based dipods [4]. Concerning closo-dodecaborate dianion, a new tetraesterified cluster have been obtained with surface initiation point intended for controlled radical polymerization. Results of these preliminary studies will be discussed. FIGURE 1. Schematic representation of oligofunctionalized boron clusters. Acknowledgements Supported in part by the National Science Center, Poland, grant 2015/16/W/ST5/00413, contributions from the Statutory Fund of IMB PAS is also gratefully acknowledged. References [1] B.P. Dash et al., New J. Chem. 2011, 35, 1955-1972. [2] S. Janczak et al., Chem. Eur. J. 2015, 21, 15118-15122. [3] J. Plešek et al., J. Organomet. Chem. 2002, 649, 181-190. [4] R. Tiwari et al., Inorg Chem. 2012, 2, 51 (1), 629-639.
Boron clusters oligopods: New tool for nanoconstruction
Carla Sardo;
2017-01-01
Abstract
Modern chemistry with refined orthogonal conjugations and highly sensitive, high resolution analytics in vitro and in vivo, facilitates development of advanced systems for biomedical application such as hybrid smart materials. These materials have the advantages of addressing multiple functions in a single tool: the system can be at the same time a drug carrier or/and have pharmacological activity itself, a diagnostic agent as well as a synergistic physical therapy element (neutron capture element, magnetic targeting and hyperthermia agent, IR sensitive element, etc.). The employement of biocompatible, nanosized scaffolds with well defined properties in terms of size, composition and surface characteristics is a priority in this field. As result of research of the last decades in the field of polyhedral boron clusters (boranes, carboranes and metallacarboranes), promising materials with unique features emerged [1]. Oligofunctionalization of boron clusters with more than one substituent (R) is of fundamental importance. The substituents R, that may be identical or differ from each other in a predetermined manner can further be used as spacer for initiation points of polymerization processes to obtain attractive molecular modules for nanoconstruction by selfassembly or to form compact, rigid, and densely populated surface-functionalized biomimetic nanosystems. Functionalization of the three vertices of o-carborane and polymerization of DNA from the surface of the obtained tripod, anchored to a solid support, have been previously reported by our group [2]. This work is now extended to the functionalization of novel oligopods of cobalt bis(1,2-dicarbollide) anion [Co(C2B9H11)2 −] and closo-dodecaborate dianion [B12H12 2−] (FIGURE 1). In the former case two approaches are tested: 1) direct functionalization of dihydroxy cobalt bis(1,2-dicarbollide) anion [3] and 2) partial degradation of functionalized at position 9 ortho-carborane followed by its reaction with cobalt salt to obtain cobalt bis(1,2- dicarbollide) based dipods [4]. Concerning closo-dodecaborate dianion, a new tetraesterified cluster have been obtained with surface initiation point intended for controlled radical polymerization. Results of these preliminary studies will be discussed. FIGURE 1. Schematic representation of oligofunctionalized boron clusters. Acknowledgements Supported in part by the National Science Center, Poland, grant 2015/16/W/ST5/00413, contributions from the Statutory Fund of IMB PAS is also gratefully acknowledged. References [1] B.P. Dash et al., New J. Chem. 2011, 35, 1955-1972. [2] S. Janczak et al., Chem. Eur. J. 2015, 21, 15118-15122. [3] J. Plešek et al., J. Organomet. Chem. 2002, 649, 181-190. [4] R. Tiwari et al., Inorg Chem. 2012, 2, 51 (1), 629-639.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
