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3 protocols using 4 cyanopentanoic acid

1

Synthesis and Characterization of Organic Compounds

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4,7-Dibromobenzo[1,2,5]thiadiazole (>98%),
(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanol (>98%),
dimethylformamide (>99.5%), 1,4-dioxane (stab. with BHT, >99%),
glycidyl
methacrylate (stab. with MEHQ, >99.5%), tetrahydrothiophene (>99%),
2-(ethylthio)ethanol (>98%), 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane
(>98%), and 3,4-dimethoxybenzylamine (>97%) were purchased from
Tokyo
Chemical Industry (TCI). Methacryloyl chloride (stab. with MEHQ,>97%),
dimethyl sulfoxide (>99.5%,anhydrous), 2-bromobenzaldehyde (98%),
4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid
(95%), hexafluorobenzene (99%), hexafluoro-2-propanol (>99%), and
4-tert-butylbenzylamine (97%) were purchased from
Sigma Aldrich. Tetrakis(triphenylphosphane)palladium (99%) and benzyl
amine (99%) were purchased from ACROS Organics. Methyl-p-tolylsulfide (97%), benzyl methacrylate (stab. with 4-Methoxy phenol,
98%), and 4,4′-azobis(4-cyanopentanoic acid) (98%) were purchased
from Alfa Aesar. Acetonitrile (>99.9%) was purchased from Honeywell.
Toluene (>99.8%), ethanol (absolute), and dichloromethane (>99%)
were
purchased from Fisher Scientific. Na2CO3 (>99.5%)
was purchased from Carl Roth. Deuterated dichloromethane (99.6%) was
purchased from Deutero GmbH. Regenerated cellulose dialysis tubing
(Sevapor 3, MWCO 3500, 16 mm diameter) was purchased from Serva.
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2

Synthesis and Characterization of Glycopolymers

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RAFT chain transfer agent 4-((((2-Carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (CCC), azobisisobutyronitrile (AIBN), 4,4’-azobis(4-cyanovaleric acid) (ABCVA), and PDSEMA were purchased from Sigma-Aldrich and used as received. Mannose ethylmethacrylate (MMA) was purchased from Omm Scientific. DIPAMA was purchased from Sigma-Aldrich and was purified by passing through a column filled with basic alumina to remove the inhibitor prior to polymerization. Anhydrous N-Methyl-2-pyrrolidone (NMP, 99.5%), and dimethylsulfoxide (DMSO, > 99%) were purchased from Sigma-Aldrich and stored with activated molecular sieves. Endotoxin level was measured using the limulus amebocyte lysate (LAL) endosafe PTS assay from Charles River.
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3

Synthesis and Characterization of Functional Polymers

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2-(Diisopropylamino) ethyl methacrylate (DPAEMA, 97%) and methacrylic acid (MAA) were obtained from Sigma-Aldrich (St. Louis, MO, USA) and passed through a basic alumina column to remove inhibitors before polymerization. 2,2’-Azobis(2-methyl-propionitrile) (AIBN, 98%), 4-((((2-carboxyethyl)thio)carbonothioyl)thio)-4-cyanopentanoic acid (95%), lysozyme (Lys, from chicken egg, >90%), 3,3’-ethylenediiminodipropylamine (EDDPA) (94%), hexamethyldisilazane (HMDS, >99%), and other solvents were obtained from Sigma-Aldrich and used as received. β-benzyl L-aspartic acid N-carboxyanhydride (BLA-NCA) was obtained from Toronto Research Chemicals (Toronto, ON, Canada). Poly(acrylic acid) (Mw ~ 50,000, 25% aqueous solution) was obtained from Polysciences, Inc.
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