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9 protocols using tetrahydrofuran thf

1

Purification and Handling of Organic Solvents

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Tetrahydrofuran (THF) was purchased from Kanto Chemical Co. Inc. (Tokyo, Japan) in the dehydrated form. N,N-Dimethylformamide (DMF) and dichloromethane (CH2Cl2) were distilled over CaH2 and phosphorus pentoxide directly before use, respectively. All imines were prepared from corresponding aldehydes and amines. Methyl acrylate was distilled directly before use. Other commercially available reagents were used without further purification. All experiments were carried out under an argon atmosphere in flame-dried glassware using standard inert techniques for introducing reagents and solvents unless otherwise noted.
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2

Recrystallization of Organic Compounds

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DDA (TCI) was recrystallized from chloroform/hexane.
2,2′-Azobis(isobutyronitrile) (AIBN; Fujifilm Wako Pure Chemical
Corp.) was recrystallized from ethanol. TMSPA (TCI), toluene (super
dehydrated, Fujifilm Wako Pure Chemical Corp.), n-octyltrichlorosilane (Sigma-Aldrich), acetone (Nacalai Tesque Inc.),
isopropyl alcohol (Nacalai Tesque Inc.), acetonitrile (Nakalai Tesque
Inc.), chloroform (Kanto Chemical Co., Inc.), and tetrahydrofuran
(THF; Kanto Chemical Co., Inc.) were used as received.
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3

Fabrication of Flexible Bioelectronic Devices

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Poly(ethylene terephthalate) (PET) film substrate, Lumirror 25T60, was purchased from Panac Co. (Tokyo, Japan). PEDOT:PSS aqueous dispersion, Clevios PH 1000 (1:2.5 PEDOT:PSS ratio), was purchased from H.C. Starck GmbH (Leverkusen, Germany). Poly (vinyl alcohol) (PVA; Mw = ~22,000), ethyl acetate, and tetrahydrofuran (THF) were purchased from Kanto Chemical Co. (Tokyo, Japan). SBS (Mw = ~140 kDa), polystyrene (PS; Mw 280000), and Zonyl® FS-300 fluorosurfactant (Zonyl) were purchased from Sigma-Aldrich, Co. (St. Louis, MO, USA). Dipropylene glycol (DPG) was purchased from Tokyo Chemical Industry Co. (Tokyo, Japan). A nylon mesh sheet, CLV-PTM-33 (Opening 40 µm, Thread diameter 40 µm, Open area 25%), was purchased from Nippon-clever Co. (Aichi, Japan). A copper sputtered conductive adhesive film (Conductive-Tape), 7836XCSB, was purchased from Sekisui Chemical Co. Ltd (Tokyo, Japan). A polyurethane-based transparent adhesive plaster, Cathereeplus, was purchased from Nichiban Co., Ltd (Tokyo, Japan). An artificial skin model, Bioskin plate, was purchased from Beaulax Co., Ltd (Saitama, Japan). A disposable gel electrode, Vitrode F, was purchased from NIHON KOHDEN Co. (Tokyo, Japan).
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4

Purification and Polymerization Protocols

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DBF was prepared according to the literature [8 (link)]. α,α’-Azobisisobutylonitrile (AIBN) (Wako Chemical, Osaka, Japan) was recrystallized from EtOH. Toluene (Wako Chemical, Osaka, Japan) was purified by washing with H2SO4 and distilled from Na wire in the presence of benzophenone. MMA (Wako Chemical, Osaka, Japan), MA (Wako Chemical, Osaka, Japan), HEMA (TCI, Tokyo, Japan), and HEA (TCI, Tokyo, Japan) were washed with aq. KOH, dried on MgSO4, and distilled under N2. Hexane (Kanto Chemical, Tokyo, Japan), tetrahydrofuran (THF) (Kanto Chemical, Tokyo, Japan), chloroform (Kanto Chemical, Tokyo, Japan), and diethyl ether (Kanto Chemical, Tokyo, Japan) were used as purchased.
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5

Synthesis of Multifunctional Monomers

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Neopentyl glycol diacrylate, 1,9-bisacryloyloxynonane, tetrahexylammonium bromide, and diethylenetriamine (DETA) were purchased from Tokyo Chemical Industry (Tokyo, Japan). Et2O, MgSO4, hexane, 5% NaOCl aq., and tetrahydrofuran (THF) were purchased from Kanto Chemical (Tokyo, Japan). All the reagents were used as received.
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6

Synthesis of Poly(Amino Acid) Derivatives

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n-Butylamine and β-benzyl-L-aspartate-N-carboxyanhydride (BLA-NCA) were obtained from NOF Corporation (Tokyo, Japan). Ethylene oxide was obtained from 3M Japan Co., Ltd. (Tokyo, Japan). Tetrahydrofuran (THF) (super dehydrated, purity >99.5%) and Toluene (super dehydrated, purity >99.5+%) were purchased from Kanto Chemical, Co., Inc. (Tokyo, Japan). Ethanol, diethyl ether, N,N-dimethylformamide (DMF) and piperidine (purity >98.0%) were purchased from Fujifilm Wako Pure Chemical, Co., Inc. (Tokyo, Japan). 1,1,3,3-Tetramethylguanidine (purity >99.0%), 2-methoxyEthanol (purity >99.0%) epichlorohydrin (purity >99.0%), triisobutylaluminum, N,N-dimethylformamide (purity >99.5%), 4-dimethylaminopyridine (purity >99.0%), 1-(3-dimethylaminopropyl)-3-ethylcordiimide hydrochloride (purity >98.0%), N-[(9H-fluoren-9-ylmethoxy)carbonyl]glycine (purity >98.0%), N-[(9H-fluoren-9-ylmethoxy)carbonyl]-L-leucine (purity >98.0%) and N-[(9H-fluoren-9-ylmethoxy)carbonyl]-L-tyrosine (purity >95.0%) were purchased from Tokyo Chemical Industry Co., Ltd. (Tokyo, Japan). Sodium hydroxide, hydrochloric acid and HEPES buffer were purchased from Sigma-Aldrich (St. Louis, MO, U.S.A). Fetal bovine serum (FBS), Dulbecco’s Modified Eagle’s Medium and Penicillin-Streptomycin were obtained from Thermo Fisher Scientific (Waltham, MA, U.S.A).
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7

NMR-Based Compound Characterization Protocol

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NMR spectra were obtained from a solution in CDCl3 using 400 MHz for 1H, 100 MHz for 13C, 376 MHz for 19F. Chemical shifts of 1H and 13C NMR are reported in ppm from tetramethylsilane (TMS) as an internal standard. Chemical shifts of 19F NMR are reported in ppm from CFCl3 as an internal standard. All data are reported as follows: chemical shifts, multiplicity (s = singlet, bs = broad singlet, d = doublet, t = triplet, q = quartet, dd = double doublet, ddd = double double doublet, m = multiplet), coupling constants (Hz), and relative integration value. HRMS experiments were measured on a double-focusing mass spectrometer with an ionization mode of EI. Melting points were measured uncorrected.
All experiments were carried out under argon atmosphere in flame-dried glassware using standard inert techniques for introducing reagents and solvents unless otherwise noted. Tetrahydrofuran (THF) was purchased from Kanto Chemical Co. Inc. as “Dehydrated”. All commercially available materials were used as received without further purification.
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8

Synthesis and Characterization of Polycaprolactone

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ε-Caprolactone (>99.0%) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD) (>98.0%) were purchased from Tokyo Chemical Industry Co.
Ltd.
(Tokyo, Japan). Ethanol (EtOH, >99.5%) and acetic acid (>99.7%)
were
purchased from Nacalai Tesque Inc. (Kyoto, Japan). Acetic anhydride
(>97%), ethyl acetate (EtOAc, >99.5%), n-hexane
(>96.0%),
chloroform (>99.0%), mEthanol (>99.8%), poly(ε-Caprolactone)
(PCL), DMSO for molecular biology, Evans blue, and sodium dodecyl
sulfate (SDS) for molecular biology were purchased from Fujifilm Wako
Pure Chemical Co. (Osaka, Japan). Dichloromethane (CH2Cl2, >99.5%) and tetrahydrofuran (THF, >99.5%) were purchased
from KANTO Chemical Co., Inc. (Tokyo, Japan) and were dried and deoxygenized
by passage through the columns of a Glass Contour Solvent System before
use. ε-Caprolactone was distilled from calcium hydride before
use. 6-Hydroxycaproic acid was synthesized as described in the literature.28 (link) EtOH was dried over 3 Å molecular sieves
before use. YCT was purchased from Recenttec K.K. (Tokyo, Japan). Chlorella sp. was purchased from Chlorella Industry Co.,
Ltd. (Tokyo, Japan). Marine Art SF-1 artificial seawater was purchased
from Osaka Yakken Co. Ltd. (Osaka, Japan).
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9

Electrodeposition of Iron Oxide Films

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Electrodeposition was conducted at 60°C in a three-electrode cell with a platinum counter electrode and a silver chloride reference electrode (Ag/AgCl, soaked in saturated KCl). An ITO slide or the ITO glass slide covered with the PS colloidal monolayer served as working electrodes. FeOx was deposited by applying a constant potential of 1.2 V (vs. Ag/AgCl) in 1 mM iron(II) chloride hexahydrate (99%, Kanto Chemical) aqueous solution at pH 5.6. 30 After removing the PS colloidal template by tetrahydrofuran (THF, 99.5%, Kanto Chemical) etching for 2 h, the films were rinsed several times with distilled water and dried in air for 30 min. [31] [32] [33]
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