Copper‐Catalyzed Azide–Alkyne Cycloaddition in the Synthesis of Polydiacetylene: “Click Glycoliposome” as Biosensors for the Specific Detection of Lectins

Abstract

Supramolecular self‐assembly of conjugated diacetylenic amphiphile‐tethered ligands photopolymerize to afford polydiacetylene (PDA) functional liposomes. Upon specific interaction with a variety of biological analytes in aqueous solution, PDA exhibits rapid colorimetric transitions. The PDA nanoassemblies, which are excellent membrane mimics, include an ene–yne polymeric reporter responsible for the chromatic transitions and the molecular recognition elements that are responsible for selective and specific binding to the biological target. A bottleneck in the fabrication of these colorimetric biosensors is the preparation of the diacetylenic monomer embedded with the recognition element of choice. In the present work, we make use of copper‐catalyzed azide–alkyne cycloaddition (CuAAC) as key step in the preparation of sugar‐coated liposome biosensors. The regioselective click ligation of the triacetylenic N‐(2‐propynyl)pentacosa‐10,12‐diynamide (NPPCDAM) with a variety of mannose‐ and lactose‐tethered azides afforded chemo‐ and regioselectively the corresponding 1,2,3‐triazole. The obtained diacetylenic monomers were incorporated efficiently into vesicles to afford functional mannose‐ and lactose‐coated glycoliposomes. The obtained PDA‐based click glycoliposomes have been characterized by using transmission electronic microscopy (TEM), dynamic light scattering (DLS), and UV/Vis spectroscopy. The efficiency of the reported approach was demonstrated by the rapid optimization of the hydrophilic spacer between the lipidic matrix and the mannose head group for the colorimetric detection of Concavalin A.

Visual Detection of pH and Biomolecular Interactions at Micromolar Concentrations Aided by a Trivalent Diacetylene-Based Vesicle

“…Following assessment of the chromism, biosensing a carbohydrate–protein interaction by 1 was undertaken. Carbohydrate–protein interactions were studied earlier with the aid of polydiacetylene polymer constructs, prepared primarily using a mono‐diacetylene monomers in millimolar concentrations . The seminal report of Charych et al on the hemagglutinin viral particle detection through a sugar‐functionalized polydiacetylene set the advantage of chromatic property beneficial to follow such ligand–receptor interactions …”

A reação "click" na síntese de 1,2,3-triazóis: aspectos químicos e aplicações

“…A reação "click" também é largamente empregada na obtenção de outros materiais como, por exemplo, polímeros, 108-111 organogéis, [123][124][125] colas/adesivos, 112,113 fios moleculares, 114 biossensores, 115 quimiossensores, 116 radiotraçadores, 117 dentre outros. Polímeros conjugados têm sido largamente explorados pela potencial aplicação em dispositivos optoeletrônicos, 165 diodos, 166 lasers orgânicos, 167 transistores de película fina 168 e dispositivos ópticos não lineares.…”

Alkyl‐mannoside derivatives: Glycolipids able to form big size aggregates

“…Because mannoside derivatives can be selectively recognized by several lectins, they could be used in the fabrication of targetable vehicles. In fact, these compounds as monomers were incorporated into synthetic liposomes or nanotubes . Their capability to interact with specific lectins, Concanavalin A (Con A) among them, was demonstrated .…”

“…In fact, these compounds as monomers were incorporated into synthetic liposomes or nanotubes . Their capability to interact with specific lectins, Concanavalin A (Con A) among them, was demonstrated . Mannosides having different structure could modulate the aggregation properties of the targetable vehicle.…”