Photoiniferter RAFT Polymerization of Optically Active Hydrophilic Vitamin B5 Analogous Methacrylamide

Abstract

Chiroptical polymers are interesting due to diverse applications in the field of chromatography, biomedicines, and catalysis. This study describes the synthesis of new types of optically active polymers of vitamin B5 analogous methacrylamide (B5AMA) using a photoiniferter polymerization approach at ambient temperatures. Enantiomers of B5AMA monomer ((R) and (S)) were prepared by the ring opening method and were characterized for their optical activity. The monomers were then polymerized by a photoiniferter polymerization approach using two different thiocarbonylthio (TCT) compounds as iniferters. Both TCTs showed controlled polymerization of B5AMA enantiomers and yielded polymers of opposite optical rotation. The enantiomeric polymers of B5AMA exhibited a complementary mirror-image Cotton effect to each other in the circular dichroism (CD) spectra, and 13C NMR analysis revealed the formation of syndiotactic polymer structures. To the best of our knowledge, this is the first study that depicts the successful synthesis of optically active macromolecules by a photoiniferter polymerization approach.

Enhanced Cryopreservation Efficacies of Ice Recrystallization Inhibiting Nanogels

“…2-Aminoethylmethacrylamide hydrochloride (AEMA) and vitamin B5 analogous methacrylamide (B5AMA) monomers were synthesized according to previously reported procedures and were analyzed using 1 H NMR and 13 C NMR (Supporting Information Figure S1). – Di­(ethylene glycol) methyl ether methacrylate (DEGMEM, 95%, Sigma-Aldrich) was passed through a small column packed with silica to remove the inhibitors contained in the reagents. 3,9-Divinyl-2,4,8,10-tetraoxaspiro[5.5]­undecane (OXAS, 98%, Sigma-Aldrich), potassium persulfate (95%, Sigma-Aldrich), 2,2'-Azobis­[2-(2-imidazolin-2-yl)­propane] Dihydrochloride (VA-044, 98%, TCI).N , N , N ′, N ′-tetramethylethylenediamine (99%, Thermo Scientific), (5-carboxytetramethylrhodamine) (TAMRA, Fisher Scientific), 4,4′-azobis­(4-cyanovaleric acid) (ACVA, 98%, Sigma-Aldrich), phosphotungstic acid (PTA, Sigma-Aldrich), 4-morpholinoethanesulfonic acid (MES monohydrate, >98.5%, Fisher), 1-ethyl-3-(3-(dimethylamino)­propyl)­carbodiimide hydrochloride (EDC, Thermo), N -hydroxysuccinimide (NHS, Thermo), 4-((((2-carboxyethyl)­thio)­carbonothioyl)­thio)-4-cyanopentanoic acid (CTA, 95%, Sigma-Aldrich), and absolute ethanol (Les Alcools de Commerce) were used as received.…”

“…In this study, we explore the synthesis, IRI activities, and cryopreservation efficacies of vitamin B5- analogous methacrylamide (B5AMA) nanogels, and their cryogenic behavior is compared with the linear poly­(B5AMA). The highly hydrophilic macromolecules of B5AMA are recently reported for water adsorption and release, for antifouling behavior, and for salt-responsive properties, owing to the hydrogen bonding capabilities of poly­(B5AMA) chains with water molecules. – Given the hygroscopic behavior of poly­(B5AMA) and their hydrogels, – poly­(B5AMA) nanogels hold significant potential as CPA for microbial and mammalian cell storage.…”

Elucidating the Role of Optical Activity of Polymers in Protein–Polymer Interactions

“…4-[[[(2-carboxyethyl) thio] thioxomethyl] thio]-4-cyano-pentanoic acid (TCT-1, 95%, Sigma-Aldrich, Oakville, ON, Canada), 3-(trimethylsilyl)-1-propanesulfonic acid sodium salt (TMSP, 97%, Sigma-Aldrich, Oakville, Canada), methanol (99.9%, Fisher, Ottawa, Canada), N,N-dimethylformamide (DMF, 99.9%, Sigma-Aldrich, Oakville, ON, Canada), ( R )-pantolactone (99%, Sigma-Aldrich, Oakville, Canada), ( S )-pantolactone (97%, Ambeed, IL, USA), deuterium oxide (99%, Cambridge Isotope Laboratories Inc., Quebec, QC, Canada), poly(ethylene glycol) methyl ether) (PEG, MN of 10000, Sigma-Aldrich, Oakville, ON, Canada), bovine serum albumin (BSA, 98%, Sigma-Aldrich, Oakville, Canada), lysozyme (LYZ, Biobasic Canada, Markham, ON, Canada), phosphate-buffered saline tablets (Millipore-Sigma, Burlington, MA, USA), and chloroform-d (99.8%, Sigma-Aldrich, Oakville, ON, Canada) were used as received. Vitamin B5 analogous methacrylamide R -(+)- and S -(−)-B5AMA monomers were synthesized according to a previously reported procedure [ 30 ] and analyzed using 1 H NMR and 13 C NMR ( Figures S1–S4 ).…”

“…We have recently reported the synthesis of biomimetic polymers of vitamin B5 analogous methacrylamide (B5AMA) through a living radical polymerization approach and have shown that the poly(B5AMA) produced is highly hydrophilic and exhibits antifouling properties when grafted on a solid support [ 28 , 29 , 30 , 31 ]. Owing to the strong hydration tendency, poly(B5AMA) of different molecular weights exhibited the depletion aggregation of bacteria [ 29 ], and surface-tethered poly(B5AMA) chains showed low fouling behaviour for both proteins and bacteria [ 28 ].…”

“…Owing to the strong hydration tendency, poly(B5AMA) of different molecular weights exhibited the depletion aggregation of bacteria [ 29 ], and surface-tethered poly(B5AMA) chains showed low fouling behaviour for both proteins and bacteria [ 28 ]. Furthermore, the polymerization of chiral R -(+)- and S -(−)-B5AMA monomers by photo-iniferter RAFT polymerization was recently reported to yield optically active polymers with complementary mirror-image cotton effects on each other [ 30 ]. Despite the known role of poly(B5AMA) as an antifouling layer when grafted on a glass surface, the solution properties of stereoisomers of poly(B5AMA) and their interactions with proteins in solution remain unknown.…”