Covalent functionalization/polycarboxylation of tungsten disulfide inorganic nanotubes (INTs-WS2)

Abstract

KEYWORDStungsten disulfide nanotubes, inorganic nanotube of tungsten disulfide (INT-WS 2 ), Vilsmeier-Haack reagents, polycarboxylation, inorganic nanotube functionalization ABSTRACT Inorganic nanotubes of tungsten disulfide (INTs-WS 2 ) are insoluble in common solvents and practically inert, hindering their usefulness in both research and commercial applications. The covalent attachment of functional species onto the surface of INT-WS 2 is a critical first step in realizing the potential that INT-WS 2 offer for high-performance materials and products. Although a few attempts have been reported regarding preparing modified nanotubes, only a limited range of surface functionalities is possible with these methods. We have developed a versatile method, based on a modified, highly electrophilic acidic VilsmeierHaack reagent, to produce covalently bonded, polycarboxylated functional WS 2 nanotubes that are dispersible in polar liquids, including water. The surface polycarboxylated shell provides a means for additional derivatization, enabling matching compatibility of derivatized nanotubes to both hydrophobic and hydrophilic materials. Nanocomposites incorporating derivatized INT-WS 2 are expected to show improved properties as a result of enhanced interfacial compatibility, made possible by the large number of classes of functionalization available through the initial polycarboxylation step.

Functionalization of Tungsten Disulfide Nanotubes with a Conformal Humin‐Like Shell

“…[ 24 ] In our group, we developed a method for surface functionalization of WS 2 INTs with polycarboxylate moieties using in-situ-generated, carboxylate-substituted Vilsmeier-Haack type iminium salts. [ 25 ] These iminium salts are electrophilic species that can be attacked by the surface sulfur atoms of the WS 2 INTs. This functionalization method was optimized by the design-of-experiment (DoE) methodology.…”

Design of Experiments: Optimizing the Polycarboxylation/Functionalization of Tungsten Disulfide Nanotubes

“…Quantification of the carboxylic acid was done indirectly by coupling 1,3-diaminopropane to the carboxylic acid using EDC as a coupling agent, followed by the Kaiser test for terminal amines [10,13].…”

“…In this context, we designed a series of experiments to optimize globally the reaction conditions for maximizing the yield of covalently functionalized tungsten disulfide inorganic fullerene-like nanotubes (WS 2 INTs). This specific functionalization reaction comprises a polycarboxylation technique [10,11], developed recently in our laboratories, that uses a modified highly electrophilic Vilsmeier-Haack reagent [12].…”

Impact of functional inorganic nanotubes f-INTs-WS2 on hemolysis, platelet function and coagulation

“…In this specific context, we recently developed a unique nanomaterial surface-engineering chemical methodology to fabricate covalently decorated functional polyacidic polyCOOH–INTs-WS 2 using Vilsmeier–Haack (VH) complex chemistry/reactivity (polyCOOH shell decoration) [ 36 ]. This novel surface engineering method enables effective covalent bonding of any desired molecule/organic species via polyCOOH shell chemical activation/reactivity that may improve and optimize any requested interfacial property of corresponding functional INTs-WS 2 ( f -INTs-WS 2 ).…”