Organophosphorus Chemistry for the Synthesis of Dendrimers

Abstract

Dendrimers are multifunctional, hyperbranched and perfectly defined macromolecules, synthesized layer after layer in an iterative manner. Besides the nature of the terminal groups responsible for most of the properties, the nature of the internal structure, and more precisely of the branching points, is also of crucial importance. For more than 15 years, we have demonstrated that the presence of phosphorus atom(s) at each branching point of the dendrimeric structure is particularly important and highly valuable for three main reasons: (i) the versatility of phosphorus chemistry that allows diversified organochemistry for the synthesis of dendrimers; (ii) the use of 31P-NMR, which is a highly valuable tool for the characterization of dendrimers; (iii) some properties (in the fields of catalysis, materials, and especially biology), that are directly connected to the nature of the internal structure and of the branching points. This review will give an overview of the methods of synthesis of phosphorus-containing dendrimers, as well on the ways to graft phosphorus derivatives as terminal groups, with emphasis on the various roles played by the chemistry of phosphorus.

Surface-Engineered Dendrimers in Gene Delivery

“…Dendrimers consist of three parts from the interior to the surface: a central core, repeated units, and surface functionalities . They are synthesized in an iterative sequence of reaction steps by convergent or divergent methods. − During dendrimer synthesis, each successive reaction step leads to an additional generation of branching, and the number of repeated cycles is defined as the dendrimer generation (denoted as G). These versatile polymers have steadily grown in popularity in miscellaneous fields, ranging from polymer chemistry to nanomedicine and biomaterials. ,,− Dendrimers have unique architecture, nanoscale size, and a high density of surface functionalities .…”

“…For example, there is an odd−even effect on gene transfection efficacy of oligoamines grafted on the polymers. The oligoamines with even-numbered repeating aminoethylene units (59) show significantly higher transfection efficacy than those with odd-numbered aminoethylene units (58) when grafted on a linear polymer. 306 This odd−even effect agreed well with the buffering capacity of these oligoamines (Figure 18).…”

Advances in the chemistry of dendrimers

“…Wide possibilities of multifunctionalisation entail the functions of dendrimers that end with P(X)Cl 2 (X = S,O). 100 Majoral et al were the first to describe dendrimers that have three or even four different types of peripheral groups. 9b These compounds were obtained by functionalisation of poly(phosphorhydrazone) dendrimers (PPH) 101 that were terminated with P(X)Cl 2 (X = S,O) groups.…”

An Azabisphosphonate-Capped Poly(phosphorhydrazone) Dendrimer for the Treatment of Endotoxin-Induced Uveitis

“…Poly(phosphorhydrazone) (PPH) dendrimers are synthesized according to a simple and efficient divergent strategy involving phosphorus-containing building blocks; and their surface functions can be easily modified to afford rationally-designed dendrimers [1]. In this regard, PPH dendrimeric structures have been designed for therapeutic applications like anti-HIV or anti-prion properties, for bio-sensing, drug delivery (transfection agents) or for the bio-imaging of blood vessels to name a few [2].…”