Hexadecameric Self-Assembled Dendrimers Built from 2′-Deoxyguanosine Derivatives

Abstract

Herein we describe the construction of hexadecameric self-assembled dendrimers (SADs) using a series of dendronized 8-(m-acetylphenyl)-2′-deoxyguanosine (mAG) subunits. The azido-substituted mAG subunits were covalently linked to alkynyl polyester dendrons using a copper-catalyzed 1,3-dipolar cycloaddition reaction. Discrete SADs are formed with high fidelity and thermal stability even with the increased steric hindrance offered by the dendrons.

Biologically derived metal organic frameworks

“…[134][135][136][137] While the above examples highlight the rich coordination modes of Ade leading in the formation of highly porous bio-MOFs, nucleobases such as Gua and their derivatives, are known to form Gquartet, and G-quadruplexes structures which have emerged as powerful tools for developing nanoscale porous materials and devices. [138][139][140][141][142][143][144][145] Verma et al reacted N9-allylguanine and N9-propargylguanine with cupric halides to form three structures ranging from discreet trinuclear motif to a mixed valence coordination polymer (Table 3, entry 16). [146] The first existing example of a crystallographically characterized nucleobase-incorporated metal-organic polyhedron (TMOP-1, Thyincorporated MOP) has also been reported by Zhou et al (Table 3, entry 17).…”

Guanosine Hydrogen‐Bonded Scaffolds: A New Way to Control the Bottom‐Up Realisation of Well‐Defined Nanoarchitectures

“…[52] Betancourt and Rivera reported the dendronization of guanosine compound 18 a to lead compound 18 b and the use of this latter derivative in the construction of well-defined and discrete SAD (Figure 15). [53] This approach relies on the propensity of guanosine derivative to form stacked G-quartets upon templation by K + ions. In particular, the authors exploited the finding that if the hydrogen atom at C 8 is replaced with an appropriate functionalised phenyl ring, only hexadecameric D 4 -symmetric assemblies are formed in the presence of KI under a wide variety of conditions.…”

Pd-catalyzed allylic substitution of purin-8-yl(allyl) acetate: Route to (E)-alkenylpurines

“…When Pd 2 dba 3 ·CHCl 3 was used, single (E)-alkenylpurine 4a has been obtained ( (Table I, Entry 5). The other tested precatalysts and ligands lead to a mixture of E-and Z-stereoisomers with isolated yields around 70% (Table I, Entries 6,7,8). Interestingly, the opposite stereochemical outcome, exclusive formation of (Z)-alkenylpurine 3a, was observed in the presence of Pd(OAc) 2 and PCy 3 (Table I, Entry 9).…”

“…Especially, various guanine/guanosine and adenine/adenosine derivatives bearing C 8 -sp 2 -carbon substituents have been prepared and studied as fluorescent/photosensitive [1][2][3][4][5] and electrochemical 6,7 marks in order to found a tool for the analysis of DNA or RNAs sequences. In addition, self-assebly of 8-aryl-2′-deoxyguanosine induced by the complexation of metal cations such as K + or Na + to dendrimers and oligomers was described 8 . Besides of photo-and electrochemical applications, C 8 -alkenyl/ arylpurines have been found as adducts that are formed by phenolic toxins 9 , antagonist of the A 3 -adenosine receptor 10 , inhibitors of glycogen synthase kinase 11 , ATP-competitive kinase 12 , fructose-1,6-bisphosphatase 13,14 , adenosine kinase 15 and others 16 .…”