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4 protocols using 4 dimethylaminopyridine

1

Synthesis of Amphiphilic Block Copolymers

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Tert-Butyl acrylate (tBA, 99%), 2-bromoisobutyryl bromide (BIBB, 98%), N,N,N,N,N-pentamethyldiethylenetriamine (PMDETA, 98%), copper(I) bromide (CuBr, 98%), trifluoroacetic acid (TFA, 99.5%), 4-dimethylaminopyridine (DMAP, 98%), and triethylamine (TEA, ultra-dry) were purchased from J&K Chemical Ltd., Shanghai, China. Styrene (St, 99%) and poly(ethylene oxide) (HO-PEO46-OH, Mn = 2050, Mw/Mn = 1.06) were purchased from Sinopharm Chemical Reagent Co., Ltd., Shanghai, China, and Sigma-Aldrich Chemical Ltd., St. Louis, MO, USA, respectively. St and tBA were purified by passing through alkaline alumina column (200–300 mesh), respectively. CuBr was purified by sequential washing with glacial acetic acid, absolute ethanol, and anhydrous ether, followed by drying in a vacuum overnight. The purified CuBr was sealed in a brown bottle for further usage. Other chemicals and solvents with analytical grade were used as received.
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2

Synthesis of Chlorothalonil Derivatives

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Chlorothalonil was purchased from Xiangtan Huayuan Fine-Chem Co. Ltd. (Xiangtan, China). 4-Dimethylaminopyridine (DMAP), N,N-dicyclohexylcarbodiimide (DCC) and carboxylic acids were purchased from J & K Chemical Ltd. (Beijing, China). Other reagents and solvents were obtained locally. All solvents were dried, and redistilled before use. The water used was redistilled and ion-free. Analytical thin-layer chromatography (TLC) was performed on silica gel GF254. Column chromatographic (CC) purification was carried out using silica gel (200–300 mesh). Above silica gel was obtained from Qingdao Haiyang Chemical Co., Ltd. (Qingdao, China). The melting points of the synthetic derivatives were determined on an X-6 apparatus (Beijing Tech., Beijing, China) and are uncorrected. Nuclear magnetic resonance (NMR) experiments were performed on an Avance 400/500 MHz instrument (Bruker, Bremerhaven, Germany). HR-MS (ESI) were obtained using a Bruker Apex-Ultra 7.0 T spectrometer. Reaction progress was monitored by thin-layer chromatography on silica gel GF-254 with detection by UV light.
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3

Synthesis and Characterization of Polymeric Nanomaterials

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1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI), triethylamine (TEA), 4-dimethylaminopyridine (DMAP), N,N-diisopropylethylamine (DIEA), N,N-dimethylacetamide (anhydrous, DMAc), dimethyl sulfoxide (anhydrous, DMSO), N,N-dimethylformamide (anhydrous, DMF), dichloromethane (anhydrous, DCM), 2,2′-azobis (2-methylpropionitrile) were purchased from J&K Scientific Ltd. (Shanghai, China). Nile Red (NiR), 1,1′-dioctadecyl-3,3,3′,3′-tetramethylindocarbocyanine perchlorate (DiL) and 1,1′-dioctadecyl-3,3,3′,3′-tetramethyl indotricarbocyanineiodide (DiR) were all obtained from Life Technologies (Shanghai, China). NLG919 was purchased from Selleck Chemghai, China). PPa was purchased from Dibai Chem Tech Co., Ltd. (Shanghai, China). Triphosgene, 4-cyano-4-(dodecylsulfanylthiocarbonyl) sulfanylpentanoic acid (CTA) and bis(2-hydroxyethyl) disulfide were purchased from TCI (Shanghai, China). Enzyme-linked immunosorbent assay (ELISA) kits were ordered from Neobioscience Technology Co., Ltd. (Shenzhen, China). Kyn, Trp and 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA) were ordered from Meilun Biotechnology Co., Ltd. (Dalian, China). The macromolecular chain transfer agent mPEG113-CTA and 2-(hexamethyleneimino) ethanol methacrylate (HMA) were synthenzied by following the similar procedure reported previously34 ,35 (link).
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4

Synthesis and Characterization of mPEG-DOX Conjugates

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mPEG-COOH (95%, weight-average molecular weight = 2000 Da) was purchased from Shanghai Biotech Co., Ltd. (Shanghai, China). Doxorubicin hydrochloride (DOX⋅HCl, 99.4%) was purchased from Beijing Huafang United Technology Co., Ltd. (Beijing, China). 1,5-Pentanediol (98%) was obtained from Chengdu Chron Chemicals Co., Ltd. (Chengdu, China). 4-Nitrophenyl chloroformate (98%) was obtained from J&K Chemical Ltd. (Beijing, China). Adipic acid dihydrazide (ADH, 98%), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (99%), 1-hydroxybenzotriazole (99%), and 4-dimethylaminopyridine (99%) were purchased from J&K Chemical Ltd. (Beijing, China). All other reagents and solvents were of analytical grade and used without further purification. Double distilled water was used throughout the experiments.
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