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8 protocols using diethylamine

1

Synthesis and Purification of Polymeric Materials

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Diethyl propylmalonate (99%), potassium hydroxide, and diethylamine (99%+) were purchased from Alfa Aesar and used without further purification. A formaldehyde solution (36.5−38.0%) was obtained from Mallinckrodt Chemicals and used as received. Concentrated sulfuric acid was purchased from Fisher and used directly. N-Isopropylacrylamide (NIPAAm), poly(ethylene glycol) methyl ether (MA-PEG), and 2-hydroxyethyl methacrylate (HEMA) were purchased from VWR. NIPAAm was recrystallized three times by hexane. MA-PEG and HEMA were purified by vacuum distillation. Trimethylene carbonate was obtained from Boehringer Ingelheim and used without further purification. All solvents were purchased from VWR and used as received.
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2

Synthesis of Functionalized Organic Compounds

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1,3,5-Tribromobenzene (98%), trimethylsilyl-acetylene (98%), trimethylsilyl azide (94%), and diethylamine (99%) were purchased from Alfa Aesar (Ward Hill, MA, USA). Sodium nitrite (97%), phosphate buffered saline (PBS) tablets, and copper(II) chloride dihydrate were obtained from EMD Chemicals (Gibbstown, NJ, USA). Glutathione (98%) was purchased from AMRESCO (Solon, OH, USA). Low molecular weight chitosan (96% deacetylated) and copper(I) iodide (99.5%) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Deionized water (18.2 MΩ·cm) was obtained from a Millipore Direct-Q water purification system (EMD Millipore, Billerica, MA, USA). Ultrahigh purity nitrogen and oxygen gases were supplied by Airgas (Denver, CO, USA). Bis(triphenylphosphine)-palladium(II) dichloride (98%) was purchased from TCI America (Portland, OR, USA). All materials were used as received without any further purification.
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3

Oligonucleotide Deprotection and Purification

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Synthesis columns containing oligonucleotides were treated previously with 10% diethylamine (Fisher) in ACN on the synthesizer. Oligonucleotides were cleaved and base-protecting groups were removed with a solution of 1:1 40% methylamine in water/30% ammonium hydroxide for 2 hours at room temperature. Cleaved and deprotected oligos were fully dried under a vacuum. Oligonucleotides containing 2’TBDMS protecting groups were dissolved in 115 μL DMSO (Sigma-Aldrich) at 65 °C. Triethylamine 60 μL (Sigma-Aldrich) followed by Triethylamine-trihydrofluoride 75 μL (Sigma-Aldrich) was added, and the whole solution was incubated for 2.5 hours at 65°C. Deprotected oligonucleotides were cooled and precipitated in a solution of 0.1 M sodium acetate in isopropanol (Sigma Aldrich). After centrifugation, the supernatants were discarded, and the pellets were dried under a vacuum. Dried oligonucleotides were dissolved in 400 μL RNase-free water and desalted using Amicon Ultra 0.5 mL 3K filter tubes (Millipore, Billerica, MA USA), followed by three RNase-free water wash rounds for 15 min at 14000 × g. Finally, desalted oligonucleotides were extracted and diluted in RNase-free water.
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4

Multimodal Peptide Separation Protocol

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Water, Optima LC/MS Grade, Acetonitrile Optima LC/MS Grade, Formic acid Optima LC/MS Grade, diethylamine, 99.5% extra pure, redistilled, ACROS Organics 1% Pharmalyte 3–10, and 2.5% Pharmalyte 8–10.5 were purchased from Fisher Scientific. Tris buffer (J. T. Baker) was prepared and pH adjusted. Acetic acid and free base l‐arginine were purchased from Sigma‐Aldrich. Peptide markers pI 8.40 and pI 9.68 were purchased from Shimura Peptide. Anolyte solution was composed of 1% v/v formic acid (pH 2.2) in water. Catholyte solution was composed of 1% v/v diethylamine (pH 12.5) in water. Mobilizer solution was 25% Acetic acid and 25% ACN in water.
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5

Oligonucleotide Deprotection and Purification

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Synthesis columns containing oligonucleotides were treated with 10% diethylamine (Fisher) in ACN on the synthesizer. Oligonucleotides were cleaved and base-protecting groups were removed with a solution of 1:1 40% methylamine in water/30% ammonium hydroxide for 2 h at room temperature. Cleaved and deprotected oligos were fully dried under a vacuum. Oligonucleotides containing 2′TBDMS protecting groups were dissolved in 115 μl DMSO (Sigma-Aldrich) at 65°C. Triethylamine 60 μl (Sigma-Aldrich) followed by Triethylamine-trihydrofluoride 75 μl (Sigma-Aldrich) was added, and the whole solution was incubated for 2.5 hours at 65°C. Deprotected oligonucleotides were cooled and precipitated in a solution of 0.1 M sodium acetate in isopropanol (Sigma Aldrich). After centrifugation, the supernatants were discarded, and the pellets were dried under a vacuum. Dried oligonucleotides were dissolved in 400 μl RNase-free water and desalted using Amicon Ultra 0.5 ml 3K filter tubes (Millipore, Billerica, MA USA), followed by three RNase-free water washes, spinning in each case for 15 min at 14 000 × g. Finally, desalted oligonucleotides were dissolved in RNase-free water.
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6

Analytical Protocols for Diverse Organic Analytes

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Solvents included dichloromethane, hexane, heptane, acetone, ethanol (≥ 99% each; Sigma-Aldrich, Canada), and HPLC-grade water (Honeywell Burdick & Jackson, Muskegon, USA), which was also used to prepare coating solutions. Analytes, including methylamine (70% in water; Arkema Inc, Canada), benzylamine (Kodak, USA), diethylamine (Fisher Scientific, USA), butylamine, pentylamine, hexylamine, octylamine and piperidine (Sigma Aldrich, Canada) were all  98% purity and used to prepare standards (10 μg/μL) in heptane. A mixture (10 μg/μL each) of pyridine (≥ 99.0%; MERCK KGaA, Germany), aniline (≥ 99.0%; BDH Inc, Canada), quinoline (≥ 99.0%; Sigma-Aldrich, Canada) and indole (≥ 99.0%; Sigma-Aldrich, Canada) was also prepared in automotive fuel purchased from a local vendor. Standards (10 µg/µL) of fluoxetine HCl, benzydamine HCl, and caffeine (each 99.9%; Sigma-Aldrich, Canada) were prepared in acetone or dichloromethane. A commercial benzydamine mouthwash was purchased from a local supplier. All other variations are described in the text.
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7

Synthesis of Functional Polymer Hydrogels

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Amino acids tyrosine and tryptophan (99% and 97% Acros, Düsseldorf, Germany), (AIBN, 98% Acrōs Germany) 2,2′-azobis(isobutyronitrile) were recrystallized from methanol, and N-isopropylacrylamide (NIPAAm, Düsseldorf) was recrystallized from distilled hexane. Vanillin (99% Düsseldorf, Germany), triethylamine (99% Merck, Darmstadt, Germany), acryloyl chloride (98% Merck, Darmstadt, Germany), formaldehyde (38% Sigma-Aldrich, Darmstadt, Germany), diethyl amine (99% Acros, Düsseldorf, Germany), Dichloromethane, dioxane, tetrahydrofuran (THF), and diethyl ether were distilled over potassium hydroxide. Other chemicals were used as received. For pH 1.68, pH 7 and pH 12.46 buffer solutions were used as purchased from Thermo Fisher (Loughborough, US).
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8

Synthesis of Ruthenium-based Catalysts

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Diethylenetriamine (C4H13N3, 99%), ruthenium(III) 2,4-pentanedionate (C15H21O6Ru, 97%), ruthenium(III) acetate (C6H9O6Ru, 99%), potassium hydrogen phosphate (K2HPO4, 98%), and potassium dihydrogen phosphate (KH2PO4, 99%) were purchased from Alfa. Sodium selenite (Na2SeO3, 99%) were purchased from Sigma-Aldrich. Zinc acetate dehydrate (C4H10O6Zn, 98%), N,N-dimethylformamide (C3H7NO, 99%), diethylamine (C4H11N, 99%), and 2-methylimidazole (C4H6N2, 99%) were purchased from Acros. Hydrazine hydrate (N2H4, 85%) were purchased from Sinopharm Chemical Reagent Co., Ltd. Carbon paper (TGP-H-06, the thickness is 0.19 mm) was purchased from Toray. All the above regents were used as received without any treatment. Ultrapure water (>18 MΩ) obtained from Milli-Q system was used throughout all the experiments.
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