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21 protocols using anhydrous dmf

1

One-Step Synthesis of Perovskite Precursor

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Methylammonium iodide (MAI) was synthesized following a one-step method reported in literature27 (link). Bphen was purchased from Nichem Fine Technology Co. Ltd. (Taiwan). PCBM and PEDOT:PSS (CLEVIOS Al 4083) were purchased from Solenne and Heraeus, respectively.
To prepare the perovskite precursor solution, MAI and lead chloride (PbCl2, 99.999%, Alfa) powder were mixed in anhydrous DMF (amine free; 99.9%, Aldrich) with a molar ratio of 3:1. The perovskite precursor solution was stirred at 70 °C overnight and then filtered through PTFE filters (0.22 μm) before use.
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2

Synthesis of Organometallic Complexes

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Chemicals were obtained from the following suppliers: diisopropylamine, 2.5 M n-butyl lithium in hexanes (Acros); EDTA, AgOTf, 4,4′-dimethyl-2,2′-bipyridine, sodium sulfide, celite 512 medium, Et3N, 2-chloro-methylpyridinium iodide, triethanolamine, anhydrous DMF, methyl chloroformate, copper(ii) acetate (Aldrich); 3-picoline (BDH Chemicals); CO2 – CP-grade with 5% CH4 (or 1% CH4) (BOC); Na2SO4, Na2CO3, NaHCO3, NaOH, HCl, KOH, ammonium hydroxide (Fisher); Zn(OAc)2·H2O, CH3CO2Na (Fisons).
Solvents for general use were obtained from Fisher. Solvents were dried by refluxing over sodium wire (C6H6, THF, toluene) or over CaH2 (CH2Cl2). DMF was dried using a Pure Solv 400-3-MD (Innovative Technology). For TRIR experiments, CH2Cl2 (99.9%, Merck) was distilled under an inert atmosphere of Ar from calcium hydride and anhydrous THF (≥99.9%, inhibitor-free, Sigma Aldrich) was used as supplied and stored in a glove box.
CD2Cl2, CD3OD, DMSO-d6 and CDCl3 were used as obtained (Aldrich) and THF-d8 was dried over potassium. Diisopropylamine was distilled from sodium hydroxide. Methyl chloroformate was distilled prior to use. n-BuLi was titrated against n-benzylbenzamide prior to use. Routine separation of porphyrins by flash chromatography was performed on a CombiFlash Rf system using 24 g RediSep Rf silica columns (Teledyne Isco), and dry-loading the samples on silica (Fluka).
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3

Synthesis and Crystallization of Pseudorotaxane

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Synthesis and crystallization of the pseudorotaxane were performed on the basis of the method described in the literature52 (link). Ruthenocene, sodium borohydride (NaBH4) and DB24C8 were purchased from Sigma-Aldrich. Anhydrous DMF, toluene, MeOH and THF were purchased from Aldrich in Sure/Seal container and were stored under N2 gas. 4-Methylbenzylamine was purchased from Alfa Aesar. 1H NMR spectra were record on Varian-Unity INOVA-500 spectrometer. The chemical shifts were referenced with respect to CHCl3H = 7.24) and CD2HCN (δH = 1.93) for 1H as internal standards. Elemental analysis was carried out with a CHN-O-Rapid elemental analyzer (Foss. Heraeus, Germany). Fast atom bombardment mass spectra (FAB-MS) were obtained with Micromass Trio 2000 using 3-nitrobenzyl alcohol as the matrix. DSC curves were recorded by a Perkin Elmer Diamond DSC instrument using heating and cooling rates of 10 °C min−1. UV-visible absorption spectra were measured using a JASCO V-630 spectrophotometer.
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4

Fmoc-based Peptide Synthesis Workflow

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Fmoc (9-fluorenyl methoxycarbonyl)–protected amino acids including Fmoc-propargyl glycine, N,N,N′,N′-tetramethyl-O-(1H-benzotriazol-1-yl) uronium hexafluorophosphate, and piperidine for SPPS were purchased from AAPPTEC Inc. (Louisville, KY). Rink amide polystyrene resin for SPPS was purchased from CEM Corporation (Matthews, NC). HPLC-grade acetonitrile (ACN) and dimethylformamide (DMF) was purchased from Thermo Fisher Scientific (Fairlawn, NJ). Copper (I) acetate, 4-azidobutanoic acid, trifluoroacetic acid (TFA), triisopropylsilane (TIS), triethylamine, anhydrous DMF, anhydrous dimethyl sulfoxide (DMSO), diisopropylethylamine, ethyl cyanohydroxyiminoacetate (Oxyma), and diisopropylcarbodiimide (DIC) were purchased from Sigma-Aldrich (St. Louis, MO).
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5

Synthesis and Characterization of Fluorescent Nanoparticles

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PMAn,
CDDP, anhydrous DMF,
silver nitrate, o-phenylenediamine, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide
hydrochloride (EDC), N,N-dimethyl
amino pyridine (DMAP), pyrene, ethylenediamine, rhodamine B isothiocyanate,
dimethyl sulfoxide (DMSO-d6), methanol-d4, and silicon wafer for FESEM were bought from
Sigma-Aldrich. PTX was purchased from Selleck Chemical. Dialysis membranes
(3.5 kDa) were purchased from Spectrum Labs. MCF7 cells were procured
from ECACC. Dulbecco’s modified Eagle’s medium (DMEM),
fetal bovine serum (FBS), LysoTracker Green DND-26, Hoechst 33342,
SlowFade Gold antifade, and Alexa Fluor-conjugated phalloidin 568
were purchased from Invitrogen. MTT reagent and tissue culture grade
DMSO were purchased from Sigma-Aldrich. 96-well flat-bottomed tissue-culture
plates were obtained from Corning.
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6

NMR Spectroscopic Analysis Protocol

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Solvents obtained from commercial sources were treated, before being used, according to procedures previously described in the literature. Anhydrous DMF was purchased from Sigma-Aldrich in a sure-seal flask. Nuclear magnetic resonance (NMR) experiments were performed on the following devices: Varian Mercury Plus (300 MHz for 1H and 75 MHz for 13C) 7.04 T and Bruker Ascend (600 MHz for 1H 150 and MHz for 13C) 14.1 T. chemical shifts (δ) were expressed in parts per million (ppm). Coupling constants are expressed in Hertz (Hz). The analysed samples were dissolved in deuterated chloroform (CDCl3). For 1H NMR spectra, TMS tetramethylsilane (0.00 ppm) was used as an internal reference, and for 13C NMR spectra, deuterated chloroform (77.0 ppm). The spectra were processed using the MestreNova 6.0 program.
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7

Synthesis of Proline-Based Heterocyclic Compounds

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A mixture of solid support proline–proline dipeptide (30 mol%), Vanillylacetone (1 mmol; Sigma Aldrich, St. Louis, MI, USA), and thiophene 3-carbaldehyde (1.2 mmol; Sigma Aldrich, USA) in anhydrous DMF (5 cm3; Sigma Aldrich, USA) under inert conditions (nitrogen gas) was stirred at 80 °C for 8 h. The reaction progress was monitored using thin-layer chromatography (TLC, Silica gel 60 F254, Merck, St. Louis, MI, USA). After the reaction, the mixture was diluted with cold water and filtered to separate the catalyst. The reaction mixture was then extracted with diethyl ether and removed under reduced pressure. The residue was separated using column chromatography (Silica gel 100–200 mesh, Merck, Rahway, NJ, USA) with a hexane–ethyl acetate mixture to afford pure compounds. The filtered catalyst was reused after drying. All the solvents and reagents were of analytical grade and obtained from Merck. The STCs were characterised using 1H, 13C nuclear magnetic resonance (NMR; JOEL 400 MHz) and CHN analysis (Thermo Scientific, Waltham, MA, USA). The synthetic scheme is shown in Figure 2.
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8

Perovskite Solar Cell Fabrication

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PEDOT:PSS Al 4083 (Clevios) was filtered with a 0.45 µm size filter before use. Methylammonium iodide (MAI) and butylammonium iodide (BAI) were purchased from Dyesol. PbI2 (99.9985%) was purchased from Alfa Aesar. Anhydrous dimethylacetamide (DMAc) (99.8%), anhydrous DMF (99.8%) and bathocuproine (BCP) (99.99%) were purchased from Sigma Aldrich. Indium tin oxide (ITO) substrates (15 Ω cm−2) were purchased from Kintec. Phenyl-C61-butyric acid methyl ester (PCBM) (99.5%) was purchased from Nano-C. Copper pellets were purchase from Kurt Lesker.
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9

Synthesis and Characterization of PEG-BZA

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PEG‐BZA was synthesized as previously described.[30] Briefly, 4‐formyl benzoic acid (0.528 g, 3.52 mmol, 2.1 eq. per amine; Sigma) was dissolved in 5 mL anhydrous DMF (Sigma) and activated with HATU (1.216 g, 3.2 mmol, 2 eq.; Sigma) and 4‐methylmorpholine (0.792 mL, 7.2 mmol, 4.5 eq.; Sigma). The reaction was allowed to stir for 5 min before the addition of 4‐arm 10 kDa PEG‐amine (4 g, 0.2 mmol; Creative PEGworks) dissolved in 5 mL DMF for a total reaction volume of 10 mL. The reaction was allowed stir at RT overnight. The final polymer was precipitated in ethyl ether (Thermo Fisher), pelleted by centrifugation at 22 000 rcf for 20 min, and re‐dissolved in Milli‐Q water. PEG‐BZA was dialyzed (MWCO: 3500 Da; Spectrum) against Milli‐Q water for 3 days at 4 °C, and dialysis water was changed two to three times per day. PEG‐BZA was lyophilized and stored at −20 °C. Modification of PEG‐BZA was estimated using 1H NMR (500 MHz). PEG‐BZA was dissolved in deuterated water (D2O; Sigma) at 10 mg mL−1. δ = 9.9 ppm (1H, s, aldehyde); δ = 7.93 and 7.82 ppm (2H each; d; benzene ring); δ = 3.56 (217H per arm; s; PEG).
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10

Zein-based Polymer Synthesis Protocol

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Alpha-zein with 3.4% moisture with molecular weight of 22–24 kD was purchased from Sigma-Aldrich (St. Louis, MO). Denatured ethyl ethanol was purchased from Acros Organics (Geel, Belgium). Anhydrous DMF, potassium carbonate, phenyl-bis(2,4,6-trimethylbenzoyl)-phosphine oxide (PO), and methacrylate anhydride were purchased from Sigma-Aldrich (St. Louis, MO). All solvents were used as received without further purification.
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