Synthesis of Zwitterionic Copolymers via Copper-Mediated Aqueous Living Radical Grafting Polymerization on Starch

Abstract

[2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) is a well-studied sulfobetaine-methacrylate as its zwitterionic structure allows the synthesis of polymers with attractive properties like antifouling and anti-polyelectrolyte behavior. In the present work, we report the Cu0-mediated living radical polymerization (Cu0-mediated LRP) of SBMA in sodium nitrate aqueous solution instead of previously reported solvents like trifluoroethanol and sodium chloride aqueous/alcoholic solution. Based on this, starch-g-polySBMA (St-g-PSBMA) was also synthesized homogeneously by using a water-soluble waxy potato starch-based macroinitiator and CuBr/hexamethylated tris(2-aminoethyl)amine (Me6TREN) as the catalyst. The structure of the macroinitiator was characterized by 1H-NMR, 13C-NMR, gHSQC, and FT-IR, while samples of PSBMA and St-g-PSBMA were characterized by 1H-NMR and FT-IR. Monomer conversion was monitored by 1H-NMR, on the basis of which the reaction kinetics were determined. Both kinetic study and GPC results indicate reasonable controlled polymerization. Furthermore, a preliminary study of the thermal response behavior was also carried through rheological tests performed on aqueous solutions of the prepared materials. Results show that branched zwitterionic polymers are more thermal-sensitive than linear ones.

Innovative Skin Product Emulsions with Enhanced Antioxidant, Antimicrobial and UV Protection Properties Containing Nanoparticles of Pure and Modified Chitosan with Encapsulated Fresh Pomegranate Juice

“…The characteristic bands of CS spectra are present at 3400 cm −1 for O-H stretching, at 3280 cm −1 attributed to the -NH 2 stretching and at 1656 cm −1 and 1584 cm −1 owing to the >C-O stretching (Amide I and II respectively) [ 50 , 51 ]. The characteristic bands of SDAEM are located at 3093 cm −1 , 3038 cm −1 and 2988 cm −1 (C-H stretch), at 1715 cm −1 (C=O stretch), at 1644 cm −1 (C-N stretch vibration), at 1186 cm −1 and 1173 cm −1 (symmetrical and asymmetrical stretch of S=O bond) [ 52 ]. In the FTIR spectra of CS-SDAEM derivative, the successful modification of CS is indicated through the appearance of a new peak recorded as a shoulder at 1718 cm −1 , which is attributed to the ester group of the monomer.…”

“…Also, the additional peak at 2.81 ppm corresponds to the methylene protons connected to the sulfonate group, whereas the rest of the methylene groups of SDAEM are present in the area between 3.5–4 ppm, but because of the occurring overlap of the peaks, it is difficult to distinguish them. Furthermore, the peak at 3.10 ppm corresponds to the six protons of the methyl groups, which belong to the quaternary amine of the monomer, while the new recorded peak at 4.65 ppm corresponds to the methyl group which is located next to the oxygen of the ester group of the monomer [ 52 ]. An interesting observation here is the absence of the peaks at 5.8 and 6.18 ppm which are witnessed in the spectrum of SDAEM.…”

Amphiphilic Copolymers Derived from Butanosolv Lignin and Acrylamide: Synthesis, Properties in Water Solution, and Potential Applications

“…The FTIR spectra of the LigBr displays a new signal at 1722 cm –1 associated to CO stretching of the α-halogen ester, enough to confirm the NMR analysis (Figure ).…”

“…Due to the need of a more sustainable economy, the synthesis of new polymeric materials from bio-based sources is attracting great interest in recent years. The synthesis of such polymeric materials can be accomplished either by the chemical modification of biomaterials such as starch, − biopolymers such as chitosan − and alginate, − or by the polymerization of bio-derived monomers, such as monosaccharides, terpenes, fatty acids, and many others. − These synthetic (co)­polymers can potentially be used in diverse application areas such as biomedicine, health care, and agriculture . Bio-based sources such as carbohydrates or lignin can also be used to make amphiphilic polymers. , The use of lignocellulosic materials is particularly attractive, as it enables the valorization of inedible plant waste.…”

pH-Sensitive Starch-Based Hydrogels: Synthesis and Effect of Molecular Components on Drug Release Behavior

“…Lately, smart hydrogels made from natural polymers have attracted increasing interest from researchers due to their biocompatibility and biodegradability [ 9 ]. The use of polysaccharides such as starch [ 10 , 11 , 12 , 13 ], cellulose [ 14 , 15 ], and chitosan [ 16 ] has been recently reported. Starch-based hydrogels can be synthesized by free-radical polymerization [ 17 , 18 ].…”