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9 protocols using anhydrous n

1

Synthesis of Novel Heterocyclic Compounds

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4-(Aminomethyl)benzonitrile
hydrochloride, acetonitrile, triethylamine, glutaric anhydride, MgSO4, formamidine acetate salt, anhydrous hydrazine, anhydrous N,N-dimethylformamide (DMF), 2-(1H-7-azabenzotriazol-1-yl)-1,1,3,3-tetramethyl uronium hexafluorophosphate
(HATU), ethyl acetate, hexane, acetic acid, dichloromethane, diethyl
ether, tetrabutylammonium salt, dimethyl sulfoxide, sodium hydroxide,
5-norbornene-2-carboxylic acid (a mixture of endo and exo isomers),
4-(dimethylamino)pyridine, di-tert-butyl dicarbonate
(Boc2O), acetone, sodium nitrite, BSA, sodium borohydride,
and Dowex 50W proton exchange resin were all purchased from Sigma
Aldrich and were used as received. The sodium salt of hyaluronic acid
(HA) 69K was purchased from Lifecore Biomedical, and glacial acetic
acid and Spectrum Spectra/Por Biotech Cellulose Ester Dialysis Membrane
Tubing (100–100,000 Da) were purchased from Fisher Scientific.
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2

Synthesis of Lead Halide Perovskite Materials

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Lead bromide (≥98%), cesium bromide
(99.99%), cesium carbonate (Cs2CO3), oleic acid
(90%), oleyl amine (≥98%), anhydrous N, N′-dimethylformamide
(DMF, 99.8%), ethyl acetate, octane (≥99%), hexane (95%), anhydrous
toluene (99.8%), and phenethylammonium bromide (PEABr, ≥98%)
were procured from Sigma-Aldrich. Poly[(9,9-dioctylfluorenyl-2,7diyl)-co-(4,4′-(N-(4-sec-butylphenyl)
diphenylamine)] (TFB, molecular weight >30,000) was purchased from
Luminescence Technology Company, Taiwan (Lumtec). All of the chemicals
were used as received without further purification.
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3

Perovskite Solar Cell Fabrication

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Bathocuproine (BCP), tetraphenylphosphonium
chloride (TPPCl), n-butyl alcohol, anhydrous N,N-dimethylformamide (DMF), and ethanol
were purchased from Sigma-Aldrich. Lead(II) iodide (PbI2) was purchased from Alfa Aesar. Phenyl-C61-butyric acid
methyl ester (PC61BM) was purchased from 1-Material Inc.
Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) and methylammonium
iodide (MAI) were purchased from Xi’an Polymer Light Technology
Corp. All materials were used as received without further purification.
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4

Synthesis and Characterization of Fluorinated Compounds

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Example 2

Overall Experimental

Bromoethane, copper(I) oxide, bromine, anhydrous N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), charcoal, and 1,4-dioxane were purchased from Sigma Aldrich. Phenothiazine and copper iodide were obtained from Acros Organics. Sodium hydride, sodium acetate, and acetic acid were purchased from Alfa Aesar. Pentafluorothiophenol and sodium pentafluoropropionate were purchased from Oakwood Chemical, iron powder from Mallinckrodt Pharmaceuticals, 2,3,4,5-tetrafluoroaniline from AK Scientific, potassium hydroxide and celite from Fisher Scientific, and ethanol from Decon Labs. All reagents were used without further purification.

Silica gel (65×250 mesh) was purchased from Sorbent Technologies, and solvents for purification were purchased from VWR International. 1H, 19F and 13C NMR spectra were obtained on 400 MHz Varian NMR spectrometers in DMSO-d6, acetone-d6 or CDCl3 purchased from Cambridge Isotope Laboratories. 19F NMR spectra were recorded in CDCl3 using hexafluorobenzene (Alfa Aesar) as an internal standard, and the chemical shifts are reported vs. CFCl3 at 0 ppm by adjusting the shift of hexafluorobenzene to −164.9 ppm. Mass spectra were obtained on an Agilent 5973 Network mass-selective detector attached to Agilent 6890N Network GC system. Elemental analyses were performed by Atlantic Microlab, Inc.

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5

Synthesis of Luminescent Lanthanide Nanoparticles

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ErCl3·6H2O (99.9%), YbCl3·6H2O (99.99%), YCl3·6H2O (99.9%), oleic acid (90%), ammonium fluoride (98%), sodium hydroxide
(98%), methanol (99.9%), anhydrous N,N-dimethylformamide, 99.8%, 1-octadecene (80%), n-hexane (95%), tetraethyl orthosilicate (99.99%), succinic anhydride
(99%), an ammonium hydroxide solution (30%), IGEPAL CO-520, (3-aminopropyl)triethoxysilane
(99%), phosphate-buffered saline tablets (PBS), 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide
(99%), and N-hydroxysulfosuccinimide (98%) were
acquired from Sigma-Aldrich and used as received.
The PBS solutions
were prepared by dissolving the tablet following the manufacturer’s
specifications. The DNA sequences were purchased from ATDBio, while
the RNA sequences were ordered from Thermo Fisher Scientific. The
ssDNA probe sequence was 5′-aminohexyl-GGCTTAATCCGACCTGACTTCTG-3′,
and the target miRNA sequence was 5′-CAGAAGUCAGGUCGGAUUAAGCC-3′.
Random sequences (noncomplementary miRNA sequences) were extracted
from sera using the miRNeasy Mini Kit from Quiagen following the manufacturer’s
protocol.
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6

Perovskite Solar Cell Fabrication

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Bathocuproine
(BCP), ammonium
metavanadate, cesium hydroxide monohydrate, anhydrous N,N-dimethylformamide (DMF), chlorobenzene, and ethanol
were purchased from Sigma-Aldrich. Lead(II) iodide (PbI2) was purchased from Alfa-Aesar. Phenyl-C61-butyric acid
methyl ester (PC61BM) was purchased from 1-Material Inc.
Methylammonium iodide (CH3NH3I) was purchased
from Xi’an Polymer Light Technology Corp. All materials are
used as received without further purification.
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7

Synthesis of Perovskite Solar Cell

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SnO2 colloid precursor (tin (IV) oxide, 15% in H2O colloidal dispersion) was obtained from Alfa Aesar, Haverhill, MA, USA. Lead iodide (PbI2, 99.99%) was acquired from TCI. Formamidinium iodide (FAI), methylammonium bromide (MABr), and methylammonium chloride (MACl) were synthesized by us. The 2,2′,7,7′-tetrakis [N, N-di(4-methoxyphenyl) amino]-9,9′-spirobifluorene (Spiro-OMeTAD) was bought from Shenzhen Feiming Co., Ltd., Shenzhen, China. Anhydrous N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), isopropanol (IPA), chlorobenzene (CB), and acetonitrile were obtained from Sigma-Aldrich. Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSID, 99.95%) and 4-tert-butylpyridine (t-BP, 98%) were also procured from Sigma-Aldrich. The Fluorine-doped SnO2-coated glass slide (FTO) was bought from Advanced Election Technology Co., Ltd., Riyadh, Saudi Arabia.
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8

Synthesis of Triptycene and Pentiptycene Diols

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Triptycene-1,4-diol (TRP) (Wiegand et al., 2014 (link)) and pentiptycene-6,13-diol (PENT) (Luo et al., 2015 (link)) were synthesized according to previous literature. Anthracene, sodium hydrosulfite, 4,4′-dichlorodiphenylsulfone (DCDPS), and 4,4′-difluorodiphenylsulfone (DFDPS) were purchased from Alfa Aesar and used as received. 1,4-benzoquinone, tetrachloro-1,4-benzoquinone, potassium carbonate (K2CO3), sodium bicarbonate, acetic acid, methanol, and 2-propanol were purchased from Sigma-Aldrich. 4,4′-biphenol (BP) and 3,3′-disulfonated-4,4′-dichlorodiphenylsulfone (SDCDPS) were purchased from Akron Polymer Systems and dried in vacuum at 110°C for 24 h before use. Anhydrous N, N-dimethylacetamide (DMAc), toluene, and hydrogen peroxide (30 wt% solution) were purchased from EMD Millipore and used as received.
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9

Synthesis of Functional Polymeric Materials

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11-Bromoundecyl methacrylate30 and 11-(4-hydroxyphenoxy)undecyl acrylate31 (link) were kindly provided by Philips Research. 4,4′-Biphenol,
sodium iodide, anhydrous N,N-dimethylformamide,
anhydrous Chloroform, thionyl chloride, anhydrous tetrahydrofuran
(THF), t-butyl-hydroquinone, 4-carboxybenzo-15-crown-5,
terephthaloyl chloride, magnesium sulfate, hydrochloric acid (37%),
and silica were purchased from Merck Life Science. Potassium carbonate
and ethanol were obtained from VWR Chemicals. Chloroform and triethylamine
were purchased from Merck KGaA. Dichloromethane and ethyl acetate
were obtained from Biosolve. Irgacure 819 was supplied by Ciba. For
permeation and sorption measurements, the gasses He (5.0 grade), CO2 (4.5 grade), N2 (5.0 grade), and Ar (5.0 grade)
were purchased from Linde gas (the Netherlands). All reagents were
used as received, without further purification.
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