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16 protocols using ethyl 2 bromoisobutyrate

1

Synthesis of Cationic Polymers via ATRP

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Methyl methacrylate (MMA) and 2-(hydroxyethyl) methacrylate (HEMA) (both Alfa Aesar, Warsaw, Poland), were dried, whereas [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMAMA, 80% aq. solution, Sigma-Aldrich, Poznan, Poland) was concentrated to a constant weight by water evaporation. Anisole (99%, Alfa Aesar, Warsaw, Poland) was desiccated using 4Å molecular sieves (Chempure, Piekary Ślaskie, Poland). Copper(I) bromide and chloride (CuBr and CuCl; both Fluka, 98%, Steinheim, Germany) were purified by stirring in glacial acetic acid, followed by filtration and washing with ethanol and diethyl ether, then dried under vacuum; 2,2′-Bipyridine (bpy), 4,4′-dinonyl-2,2′-dipyridyl (dNbpy, 97%), tetrahydrofuran (THF), pyridine (99%), α-bromoisobutyrate bromide (BIBB, 98%), ethyl 2-bromoisobutyrate (EBiB), potassium clavunate (KCLV), and sodium p-aminosalicylate (NaPAS) were used as received (all Sigma Aldrich, Poznan, Poland).
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2

Zwitterionic Polyethersulfone Membrane Synthesis

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Polyethersulfone (PES) in pellet form (Solvay Specialty Polymers), N-Methyl-2-pyrrolidone (purity >99.5%, RCl-Labscan) and polyvinylpyrrolidone (PVP K30, Sigma-Aldrich) as additive were used for fabrication of membrane substrate. 1,3-phenylenediamine (MPD) and trimesoyl chloride (TMC) purchased from Sigma Aldrich were used to form a PA layer on top of the PES substrate. To synthesize zwitterion properties polymer, 2-(dimethylamino)ethyl methacrylate (DMAEMA, 95%), 2-bromoisobutyrate bromide, diisobutylaluminium hydride (1.0 M in toluene), ethyl 2-bromoisobutyrate (EBiB, 98%), 1,3-propanesultone (99%), dipyridyl (Bpy, AR), 2-bromoisobutyryl bromide (98%), copper(I) bromide (CuBr, 99%) and 1-hexyl-3-methylimidazolium chloride (HMImCl) were purchased from Sigma Aldrich. Diethyl ether was purchased from RCl-Labscan. Sodium chloride (NaCl, Merck) was used as test solute for membrane flux and rejection determination. The feed solution containing the respective test solute was prepared by dissolving the solute in deionized (DI) water.
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3

Synthesis of Functionalized Polymers

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Cysteine (NH2‐SS‐NH2) was obtained from PerkinElmer. Dichloromethane and dimethylformamide were purchased from Sinopharm. Triethylamine, methacryloyl chloride, Copper(I) bromide, ethyl 2‐bromoisobutyrate, 1,2,3,4‐tetrahydronaphthalene, oleylamine, HAuCl4•3H2O, toluene, Elacridar, and trifluoroacetic acid were purchased from Sigma‐Aldrich. Tert‐butyl methacrylate and ligand N,N,N′,N′,N″‐pentamethyldiethylenetriamine were obtained from Aladdin (Aladdin Chemistry Co., Ltd.).
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4

Synthesis of Poly(γ-CD-g-HEMA) Copolymers

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γ-CD (Wako, Japan) and PPO-PEO-PPO (comprised of a central block of 90 PEO units and two flank blocks of 5 PO units having Mn = 4580 (Zhejiang Huangma Chemical Industry Group Co., Ltd, China)) were used as received without further purification. 2-Hydroxyethyl methacrylate (HEMA) (TCI, Japan) was passed over a short basic alumina column to remove the inhibitor before polymerization. N,N,N’,N”,N”-penta-methyldiethylenetriamine (PMDETA) and ethyl 2-bromoisobutyrate were purchased from Sigma, USA. Both 2-bromoisobutyryl bromide and 4-dimethylaminopyridine (DMAP) were available from Alfa Aesar, USA. Triethylamine (TEA) (VAS Chemical Reagents Company, China) was refluxed with p-toluenesulfonyl chloride and distilled under vacuum. Copper(I) chloride (Cu(I)Cl) was prepared from CuCl2, purified by stirring in hydrochloric acid, washed with methanol and finally dried under vacuum prior to use. CH2Cl2 was stirred with CaH2 and distilled under reduced pressure. DMF was supplied by Sinopharm Chemical Reagent Company, China and used without further purification. All other solvents and reagents were of analytical grade.
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5

Synthesis of Functional Polymers via ATRP

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The methyl methacrylate (MMA; Alfa Aesar, Warsaw, Poland) was dried using molecular sieves (type 4Å, Chempur, Piekary Śląskie, Poland). The [2-(methacryloyloxy)ethyl]-trimethylammonium chloride (TMAMA/Cl; 80% aq. solution, Sigma-Aldrich, Poznań, Poland) was dried to a constant weight under reduced pressure. Methanol and tetrahydrofuran (THF) were purchased from Chempur (Piekary Śląskie, Poland) and dried over the same molecular sieves as MMA. Copper(I) bromide (CuBr; Fluka, 98%, Steinheim, Germany) was purified using a procedure described previously in the literature [42 (link)]. N,N,N′,N,N″-pentamethyldiethylenetriamine (PMDETA, 98%), ethyl 2-bromoisobutyrate (EBiB, 98%), potassium clavulanate (KCLV), and bis(trifluoromethane)sulfonimide lithium salt (LiTf2N) were obtained from Sigma Aldrich (Poznań, Polska). Sodium p-aminosalicylate (NaPAS, 98%), sodium piperacillin (NaPIP, 99%), and sodium fusidate (NaFUS, 98.8%) were purchased from Alfa Aesar (Warsaw, Poland) and used without further purification.
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6

Synthesis of Organic Photofunctional Materials

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ZrCl4, DMF,
acetic acid, 2-aminoterephthalic acid, toluene, chlorodimethylsilane,
10-undecenyl 2-bromoisobutyrate (95%), Karstedt’s catalyst
in xylene (99%), anisole, ethyl 2-bromoisobutyrate, lauryl methacrylate
(LMA, 98%), CuI, CuBr, and N,N,N′,N′,N″-PMDETA
(99%) were purchased from Sigma-Aldrich, Germany. Naphthalene (Nap),
fluorine (Flu), acenaphthylene (Ace), anthracene (Ant), phenanthrene
(Phe), and pyrene (Pyr) were purchased from Merck (Darmstadt, Germany).
CuBr (98%) was agitated in glacial acetic acid for 12 h before being
filtered and washed with ethanol, followed by drying under vacuum.
The purified CuBr powder was stored in a desiccator. LMA was dissolved
in tetrahydrofuran (THF); then, it was passed through a silica gel
column to eliminate the inhibitor, and then, THF was removed under
high vacuum.
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7

Surface Functionalization of Stainless Steel

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Foils (100 mm × 100 mm) of 316 SS and 316L polished SS (Goodfellow, Pittsburgh, PA, USA) were cut into 10 mm × 10 mm coupons and a 0.8 mm hole was drilled in one corner. 316L SS 20-gauge wire was obtained from Beadlon (Valley Township, PA, USA). Oligo(ethylene glycol) methacrylate (OEGMA), Cu(I)Br, 2,2′-bipyridyl, ethyl 2-bromoisobutyrate, dopamine hydrochloride, anhydrous pyridine, hydrogen hexachloroplatinate (IV) hexahydrate, anhydrous dimethylformamide (DMF), 10-undecen-1-ol, dimethylchlorosilane, 1-ethyl-3-(3-N,N-dimethylaminopropyl)carbodiimide hydrochloride, 2-bromoisobutyryl bromide and N-hydroxysuccinimide (NHS) were purchased from Sigma-Aldrich (Milwaukee, WI, USA). Succinic anhydride was purchased from Alfa Aesar (Wardhill, MA, USA). For the polymerization of OEGMA, DI H2O and methanol (MeOH) (VWR, Atlanta, GA, USA) were degassed by bubbling a stream of argon through the solvents for 3 h. Peptide ligands (RGD (GRGDSPC) or RDG (GRDGSPC) or RGD-FITC (GRGDSPK conjugated to fluorescein isothiocyanate(FITC))) were custom synthesized by GenScript (Piscataway, NJ, USA)
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8

Synthesis of Multifunctional Polymer Materials

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N-Isopropylacrylamide (NIPAm, 97%), tert-butyl acrylate (tBA, 98%), β-cyclodextrin
(β-CD), 2-bromoisobutyryl bromide (BiBB, 98%), 1-methyl-2-pyrrolidone
(NMP), dichloromethane (DCM), copper powder (Cu0, 99.7%,
45 cm2 g–1), crystal violet (CV, ≥90.0%),
ethyl 2-bromoisobutyrate (EBiB, 98%), copper(I) bromide (CuBr, ≥99.995%),
copper(II) bromide (CuBr2, ≥99.995%), potassium
fluoride (KF, 99%), trifluoroacetic acid (TFA, ≥98%), spermidine
(99%), basic alumina, and chloroform-d (CDCl3) were obtained
from Sigma-Aldrich. The (2-trimetylsiloxy)ethyl methacrylate (HEMA-TMS)
was purchased from Scientific Polymer Products. The tris(2-dimethylaminoethyl)amine
(Me6TREN, ≥99%), gadolinium(III) chloride hexahydrate
(GdCl3·6H2O, 99%), anisole (99%), and N,N-dimethylformamide
(DMF, 99%) were purchased from Alfa Aesar. HNO3 (70%, trace
metal grade) and H2O2 (30%, ACS grade) were
purchased from Fisher Scientific. Dialysis bags with desired molecular
weight cutoffs were purchased from Spectrum Lab (Spectra/Por 7). The tBA monomer was purified by passing through basic alumina
to remove inhibitors. Other chemicals were used as received without
further purification.
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9

Synthesis of Functional Polymer Nanoparticles

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N-Isopropylacrylamide
(NIPAm,
97%), 2-(dimethyl amino)ethyl methacrylate (DMAEMA, 98%), β-cyclodextrin
(β-CD), 2-bromoisobutyryl bromide (BiBB, 98%), 1-methyl-2-pyrrolidone
(NMP), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA, 97%),
dichloromethane (DCM), copper powder (Cu0, 99.7%, 45 cm2 g–1), Rose Bengal (RB, 95%), Crystal violet
(CV, ≥90.0%), diethylenetriaminepentaacetic acid gadolinium(III)
dihydrogen salt (Gd-DTPA, 97%), ethyl 2-bromoisobutyrate (EBiB, 98%),
copper(I) bromide (CuBr, ≥99.95%), copper(II) bromide (CuBr2, ≥99.995%), potassium fluoride (KF, 99%), basic alumina,
and chloroform-d (CDCl3) were obtained from Sigma-Aldrich.
(2-Trimethylsiloxy)ethyl methacrylate (HEMA-TMS) was purchased from
Scientific Polymer Products. Tris(2-dimethylaminoethyl) amine (Me6TREN, ≥99%), gadolinium(III) chloride hexahydrate (GdCl3·6H2O, 99%), anisole (99%), and N,N-dimethylformamide (DMF, 99%) were purchased from
Alfa Aesar. HNO3 (70%, trace metal grade), Silwet L-77,
and H2O2 (30%, ACS grade) were purchased from
Fisher Scientific. Dialysis bags with desired molecular weight cutoffs
were purchased from Spectrum lab (Spectra/Por 7). The DMAEMA monomer
was purified by passing it through basic alumina to remove the inhibitor.
Other chemicals were used as-received without further purification.
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10

Grafting PMMA onto Paper Pulp

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Paper pulp used in this study were kindly provided by Chung–Hua Paper Inc., Taiwan (LBKP grade). Cupric bromide (CuBr2, 99%) 4,4–dimethylaminopyridine (DMAP, 99%), 2–bromoisobutyryl bromide (BiB, 97%), 2,2,6,6–tetramethylpiperidin–1–yl)oxyl (TEMPO, 98%), 2,2′–azobis(2–methylpropionitrile) (AIBN, 98%), ethyl 2–bromoisobutyrate (EBiB, 99%), N,N,N’,N´´,N´´–pentamethyldiethylenetriamine (PMDETA, 99%), methyl methacrylate (MMA, 99%), and triethylamine (TEA, 99.5%) were purchased from Sigma–Aldrich (Darmstadt, Germany). Sodium hydroxide (NaOH, 96%), hydrochloric acid solution (HCl(aq), 35%), sodium bromide (NaBr, 99%), and sodium hypochlorite aqueous (NaClO(aq), 12%) were purchased from Showa Corporation (Saitama, Japan). Commercial PMMA with average molecular weight (Mn) of 600,000 g/mol was purchased from Polyscience (Niles, IL, USA). All solvents were used without any further purification.
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