A “Clickable” Hybrid Nanocluster of Cubic Symmetry

Star-Shaped and Linear POSS-Polylactide Hybrid Copolymers

“…Polyhedral oligomeric silsesquioxanes (POSS) present a unique class of inorganic structures that can be exploited in generation of hybrid polymer systems of advantageous properties [1,2,3,4,5,6]. Among these, cube octameric silsesquioxanes (RSiO 1.5 ) 8 have been recently covalently bonded to peptide and glycoside moieties as well as such polymers as e.g., polylactide (PLA), poly(ethylene oxide) (PEO), glycomethacrylate or poly(caprolactone) (PCL) [2,7,8,9,10].…”

Direct Enzymatic Branch‐End Extension of Glycocluster‐Presented Glycans: An Effective Strategy for Programming Glycan Bioactivity

“…[12,13] Ester-protected lactosyla zide 22 was also synthesized as previously reported, [14] and the click reaction [15] with terminal acetylenes of scaffolds 8,12,15,17,19,a nd 21 was carriedo ut by using CuSO 4 ands odium ascorbate in DMF/H 2 O by MW at 80 8Cf or 15 min, to afford 23,25,27,29,31,a nd 33, with hydroxyl groups still protected. [12,13] Ester-protected lactosyla zide 22 was also synthesized as previously reported, [14] and the click reaction [15] with terminal acetylenes of scaffolds 8,12,15,17,19,a nd 21 was carriedo ut by using CuSO 4 ands odium ascorbate in DMF/H 2 O by MW at 80 8Cf or 15 min, to afford 23,25,27,29,31,a nd 33, with hydroxyl groups still protected.…”

“…Given the differences in spatial accessibility of the two lectin sites per B-chaina tc oncentrations of mgmL À1 and higher (with the Tyrs ite fully,t he Trp site only partially accessible), [20] the Tyrs ite was analyzed. [5,22] Remarkably,t he method can be applied to spherical glyconanoclusters, [23] facilitating work with vesicle-presented glycodendrimerst oy ield programmable cell surfaces and natural or rationally engineered lectins. When running docking protocols and DOSYe xperiments to determine the diffusion coefficients of complexes,t he tetravalent compound wasf ound to associate with am aximum of two lectin molecules (data not shown).…”

“…Generalprocedure Peracetylated glycoconjugate 23,25,27,29,31, or 33 was dissolved in anhydrous methanol and NaOMe (1 m)w as added, and the solution was stirred until TLC showed full deacetylation. The solution was then neutralized (Amberlist-15, H +)a nd filtered.…”

“…In the G2 series, the ether-type dialkyne 17, 19,a nd 21 were synthesized as previously reported (see the Supporting Information). [12,13] Ester-protected lactosyla zide 22 was also synthesized as previously reported, [14] and the click reaction [15] with terminal acetylenes of scaffolds 8,12,15,17,19,a nd 21 was carriedo ut by using CuSO 4 ands odium ascorbate in DMF/H 2 O by MW at 80 8Cf or 15 min, to afford 23,25,27,29,31,a nd 33, with hydroxyl groups still protected. Deacetylation was carried out with NaOMe in MeOH to yield the free glycoclusters 24,26,28,30,32,a nd 34 (Scheme 1), which were readily soluble in water.…”