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6 protocols using trifluorotoluene

1

Synthesis of Fluorine-Rich Dioxolane Compound

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Example 4

Synthesis of 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-(2,2,2-trifluoroethoxy)-1,3-dioxolane. Tris(2,2,2-trifluoroethyl)orthoformate (1.4 eq., 48 mmol, 15 g, SynQuest Laboratories) and 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecane-1,2-diol (14 g, 34 mmol, 1 eq., Shanghai Chemhere Co., Ltd.) was dissolved in 240 mL of anhydrous cyclohexane (Aldrich) in a round bottom flask. The resulting solution was slightly cloudy and trifluorotoluene (Aldrich) was added dropwise until the solution was clear (5 mL). A catalytic amount of p-toluenesulfonic acid (Aldrich) was added to the flask along with a Teflon coated magnetic stirbar. The flask was fitted with a Dean-Stark distillation head. The reaction was slowly heated to reflux and the trifluoroethanol was removed by azeotropic distillation at a boiling point of 65° C. After 1 hour, the reaction was complete and the flask was cooled to room temperature. The reaction mixture was concentrated at reduced pressure on a rotary evaporator. The residual mixture was purified by fractional distillation under reduced pressure (b.p.=85-104° C. at 0.05 mmHg), providing the title compound in 44% isolated yield. The product was verified by characteristic peaks in the 1H NMR and by molecular ion in ESI/TOF mass spectroscopy (M+1, 519.1, 520.1 m/z).

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2

Synthesis of 4-(Trifluorooctyloxy)Dioxolane

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Example 2

4-(((3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)oxy)methyl)-2-(2,2,2-trifluoroethoxy)-1,3-dioxolane. Tris(2,2,2-trifluoroethyl)orthoformate (50 g, 161 mmol, SynQuest Laboratories) and 3-[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)oxy]-1,2-propanediol (25 g, 57 mmol, Wako Chemicals) was dissolved in 800 mL of anhydrous cyclohexane (Aldrich) in a round bottom flask. Trifluorotoluene (Aldrich) was added in 5 mL portions until the solution was clear (30 mL). A catalytic amount of p-toluenesulfonic acid (Aldrich) was added to the flask along with a Teflon coated magnetic stirbar. The flask was fitted with a Dean-Stark distillation head. The reaction was slowly heated to reflux and the trifluoroethanol was removed by azeotropic distillation at a boiling point of 65° C. After 3 hours, the reaction was complete and the flask was cooled to room temperature. The reaction mixture was concentrated at reduced pressure on a rotary evaporator. The residual was purified by fractional distillation under reduced pressure (b.p.=95-100° C. at 0.05 mmHg), providing the title compound in 74% isolated yield.

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3

Synthesis of Superhydrophobic OPSZ Coatings

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Durazane™ 1500RC (Merck, Germany), consisting of 3-aminopropyltriethoxysilane-substituted polymethyl-(hydro)/polymethylsilazane, was used as the OPSZ precursor (Mw = 1745, PDI = 22), and its molecular structure is illustrated in Scheme 1A. 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane (FAS-17) was obtained from Sooyang Chemtec (Gamgok-myeon, Korea). Toluene (99.8%), tetrahydrofuran (THF, ≥99%), trifluoroToluene (TFT, ≥99%), and hexamethyldisilazane (≥99%) were purchased from Sigma Aldrich (St. Louis, MO, USA). Acetone (99.5%), ethanol (99.5%), and hydrochloric acid (37 wt%) were supplied by Samchun Chemical (Korea). All the chemicals were used as received without further purification.
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4

Commercial γ-AlOOH Filtration Media Functionalization

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A commercial γ-AlOOH filtration media
4603 was provided by Ahlstrom Filtration LLC (Mt Holly Springs, PA).
The filter media was used without further pretreatment. Oxygen plasma
treatment was accomplished using a Harrick Plasma Cleaner PDC-001.
Commercial perfluorosilanes and 3-aminopropyl trimethoxysilane were
obtained from Gelest Inc. (Morrisville, PA) and used in the as-received
form. PFOS, PFOA, trifluorotoluene, Novec 7100, and ethanol were obtained
from Sigma-Aldrich (St. Louis, MO) and used without any further purification.
Reagents for synthesis were obtained from Sigma-Aldrich or Oakwood
Chemicals and used as received. Anhydrous solvents were purchased
from Sigma-Aldrich. Filtrasorb 300 granular activated carbon was obtained
from Calgon Carbon Corporation (Moon Township, PA).
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5

Synthesis of Epoxy-Functionalized Perfluorobutane

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1,4-bis(2′,3′-epoxypropyl)perfluorobutane (BEPFB) was provided by TOSOH Finechemical Corporation (Shunan, Japan). Lithium bromide (LiBr), acetone (analytical grade), hexylamine, hexamethylenediamine, 1,2,7,8-diepoxyoctane, Dimethylformamide (DMF), Dimethyl Sulfoxide (DMSO), acetonitrile, ethyl acetate, dimethyl carbonate, trifluorotoluene, and 1,4-dioxane were purchased from Sigma-Aldrich. The deuterated solvents were purchased from Euroiso-top (purity > 99.8%).
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6

Synthesis and Characterization of Lipid-based siRNA Delivery System

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AMD3100 was purchased from BioChemPartner (Shanghai, China). N,N’-Hexamethylenebisacrylamide (HMBA) was from Pfaltz & Bauer (Waterbury, CT). mPEG-Acrylamide (2 kDa) was purchased from Creative PEGWorks (Winston-Salem, NC). Cholesteryl chloroformate, 2,3,5,6-tetrafluoro-p-toluic acid (TFTA), 4-(dimethylamino) pyridine (DMAP), and trifluorotoluene were obtained from Sigma-Aldrich (St. Louis, MO). N-Hydroxysuccinimide (NHS), N, N’-dicyclohexylcarbodiimide (DCC), and N,N-diisopropylethylamine (DIPEA) were from Acros Organics (Fair Lawn, NJ). Cyanine3 NHS ester was purchased from Lumiprobe (Hunt Valley, MD). Dulbecco’s Phosphate Buffered Saline (PBS), Dulbecco’s Modified Eagle Medium (DMEM), Fetal Bovine Serum (FBS) and penicillin/streptomycin (Pen-Strep) solution were obtained from Thermo Scientific (Waltham, MA). siRNA targeting PLK1 (siPLK1, sequence: 5’-CAACACGCCUGAUUCUCUA-3’), scramble siRNA nonspecific to any mouse gene (siScr, sequence: 5’-AUGAACGUGAAUUGCUCAA-3’), GE Healthcare Dharmacon (Lafayette, CO). TRIzol® reagent was purchased from Life Technologies (Carlsbad, CA).
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