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7 protocols using 1 4 dibromobenzene

1

GC-MS Analysis of Metabolites

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Pure standards of n-alkanes (from n-C9 to n-C30) for system evaluation and linear retention indexes (IT), internal standards (ISs) 4-chlorophenylalanine and 1,4-dibromobenzene were from Merck (Milan, Italy).
The mixture of n-alkanes for the IT solution was prepared in cyclohexane at a concentration of 100 mg/L; internal standards (ISs) solutions were prepared in dichloromethane (GC grade) at a concentration of 4 mg/mL.
Pure standards for identity confirmation of pyruvic acid, malonic acid, phosphoric acid, succinic acid, glyceric acid, fumaric acid, malic acid, citric acid, Alanine-Ala, Aspartic acid-Asp, Glutamic acid-Glu, Glycine-Gln, Isoleucine-Ile, Leucine-Leu, Methionine-Met, Phenylalanine-Phe, Proline-Pro, Serine-Ser, Threonine-Thr, Tryptophan-Trp, Tyrosine-Tyr, Valine-Val, glycerol, xylitol, mannitol, myo-inositol, fructose, glucose, and the internal standards (ISs), 4-chlorophenyl alanine (quality control–QC for derivatization), and 1,4-dibromobenzene (QC for GC normalization) were purchased from Merck (Milan, Italy).
Derivatization reagents and HPLC grade solvents: O-methyl hydroxylamine hydrochloride (MOX), (N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) methanol, pyridine, n-hexane, cyclohexane, dichloromethane, and toluene were also obtained from Merck.
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2

Synthesis of Halogenated Aromatic Compounds

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Tris(4-bromophenyl)amine (98%), p-phenylenediamine (99%), 1,4-dibromobenzene (95%), bis(dibenzylideneacetone)palladium(0)
(Pd(dba)2), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl
(XPhos, 97%), sodium tert-butoxide (NaOtBu, 97%),
3,5-dibromobenzoic acid, and all solvents of A.R and C.R. grades were
purchased from Merck and used as received. For dye absorbance studies,
Acid Blue 92 (40%), Methylene Blue (82%), Congo Red (35%), Ethyl Orange
(90%), and Direct Blue 15 (40%) were purchased from Merck and used
as received.
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3

Comprehensive Metabolite Profiling Protocol

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Pure standards of n-alkanes (from n-C9 to n-C25) for system evaluation and linear retention indexes (I T ) determination and α-tujone for volatiles internal standardization (IS) were from Merck (Milan, Italy).
The mixture of n-alkanes for the I T solution was prepared in cyclohexane at a concentration of 100 mg/L; internal standard (IS) α-thujone solution was prepared in diethyl phthalate (Sigma Aldrich 99% of purity) at a concentration of 100 mg/L. Pure standards for identity confirmation of pyruvic acid, lactic acid, malonic acid, acetoacetic acid, phosphoric acid, succinic acid, glyceric acid, fumaric acid, malic acid, citric acid, Alanine-Ala, Asparagine-Asn, Aspartic acid-Asp, Cysteine-Cys, Glutamic acid-Glu, Glycine-Gln, Isoleucine-Ile, Leucine-Leu, Lysine-Lys, Methionine-Met, Ornithine-Orn, Phenylalanine-Phe, Proline-Pro, Serine-Ser, Threonine-Thr, Tryptophan-Trp, Tyrosine-Tyr, Valine-Val, glycerol, xylitol, mannitol, myo-inositol, fructose, glucose, saccharose, and the internal standards (IS), 4-chlorophenylalanine (quality control -QC for derivatization) and 1,4-dibromobenzene (QC for GC normalization), were from Merck (Milan, Italy).
Derivatization reagents and HPLC grade solvents: O-methylhydroxylamine hydro-chloride (MOX), (N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) methanol, pyridine, n-hexane, di-chloromethane, and toluene were from Merck (Milan, Italy).
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4

Synthesis of Nitrophenyl-Substituted Triarylamine

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1,4-Dibromobenzene, 4-bromo-N,N-bis(trimethylsilyl)aniline, p-toluenesulfonic acid monohydrate (PTSA), n-butyllithium, anhydrous N,N-dimethylacetamide (DMAc), anhydrous calcium sulfate were purchased from Sigma-Aldrich (Milwaukee, WI, USA). 3-Nitrophenylboronic acid, 4-aminophenylboronic acid pinacol ester, bis(4-formylphenyl)phenylamine (TPA) and tetrabutylammonium hexafluorophosphate (TBAHFP) were obtained from AK Scientific, Inc. (San Francisco, USA). Potassium carbonate, chloroform, n-hexane, toluene, 1,4-dioxane, dichloromethane and tetrahydrofuran were purchased from Merck (Darmstadt, Germany). Except for THF, which was dried over sodium using benzophenone as indicator under nitrogen atmosphere and distilled immediately before its use, all reagents and solvents were used as received without further purification.
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5

Synthesis of Substituted Phenylacetylenes

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The polymerization solvent, toluene (Fujifilm Wako Pure Chemical Co., Ltd., Osaka, Japan), was purified twice by distillation in the presence of CaH2 (Fujifilm Wako Pure Chemical Co., Ltd.). The main catalyst, TaCl5 (99.999%, Sigma-Aldrich, St. Louis, Missouri, USA), was used without further purification, while the cocatalyst, n-Bu4Sn (Fujifilm Wako Pure Chemical Co., Ltd.), was used after distillation in the presence of CaH2. Phenylacetylene (Sigma-Aldrich), 1,4-dibromobenzene, 1-bromo-4-tert-butylbenzene, triethylamine, triphenylphosphine, copper(i) iodide, dichlorobis(triphenylphosphine)palladium(ii), n-butyllithium, trifluoroacetic acid (TFA), chlorotrimethylsilane, 2-methyl-3-butyn-2-ol, sodium hydride, aqueous sodium nitrate, and other common solvents (Fujifilm Wako Pure Chemical Co., Ltd.) were used without further purification. 1-(p-Trimethylsilyl)phenyl-2-(p-trimethylsilyl)Phenylacetylene (1a),23 (link) 1-phenyl-2-(p-tert-butyl)Phenylacetylene (1b),11 (link) and 1-phenyl-2-(p-trimethylsilyl)Phenylacetylene (1c)10 (link) were synthesized according to the methods reported in literature.
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6

Anhydrous Chromium Reagents Synthesis

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Unless otherwise stated all manipulations were carried out in an airfree nitrogen glovebox or on a nitrogen Schlenk line using standard airfree Schlenk techniques and glassware. Solvents including DMF, acetonitrile, and ether were dried using a solvent purification still under Argon, filtered over alumina, and stored over 4 Å molecular sieves until used. Anhydrous CrCl2 was purchased from Alfa Aesar and used without further purification. Chromium metal (50 mesh) was purchased from Sigma-Aldrich. ICP standards were purchased from High Purity Standards. Trace metal grade nitric acid and hydrogen peroxide were purchased from Sigma-Aldrich. 1,4-dibromo benzene, 1,3,5-tribromo benzene, and 2-propanethiol were purchased from Sigma-Aldrich.
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7

Diverse Halogenated Compounds: Preparation and Analysis

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PCE, TCE, cDCE, trans-dichloroethene (tDCE) vinyl chloride (VC), ethene (ETH), 2,4,6-trichlorophenol (2,4,6-TCP), 2,6-dichlorophenol (2,6-DCP), 2,4- dichlorophenol (2,4-DCP), chlorophenol (CP), 2,6-DBP, 3-bromophenol (3-BP), 2-bromophenol (2-BP), 2,4,6-triiodophenol (2,4,6-TIP), 2,6-diiodophenol (2,6-DIP), 2,4-diiodophenol (2,4-DIP), 2-iodophenol (2-IP) and 4-iodophenol (4-IP), phenol, 1,4-dibromobenzene (1,4-DBB), bromobenzene (BB), and benzene were purchased from Sigma-Aldrich. Sulfate (0.5 M) and lactate (0.5 M) stock solutions were prepared by filter sterilization (syringe filter, 0.2 µm, mdimembrane, Ambala Cantt, India). All other (in)organic chemicals were of analytical grade.
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