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11 protocols using dmso d6

1

Quantifying Chiral Ligand Density on CsPbBr3 QDs

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To prepare samples for 1H-NMR measurements, pellets obtained from purification of the chiral particles were dried under vacuum for 1–2 h, then weighed and digested in deuterated dimethyl sulfoxide (DMSO-d6; Cambridge Isotope Laboratories, 99.9% D). A 0.02 M stock solution of ferrocene (Thermo Scientific, 99%) in DMSO-d6 was added to the digested pellet solution at 0.004 M, and was used to calibrate the intensity of the NMR spectra. NMR measurements were then collected using a Bruker Advance 400 MHz spectrometer. From the ferrocene-calibrated spectra, the total mass of ligands in solution could be calculated, and subtracted from the net pellet mass to yield the mass of CsPbBr3. Assuming the particles to possess a cubical shape, the total number of QDs in the sample and hence total surface area could be calculated from the known volume and mass of the unit cell of orthorhombic CsPbBr3. Combining the mass of ligand determined from the NMR measurements with this surface area allows the density of both chiral and achiral ligands to be estimated.
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2

LC-MS/MS and NMR Analysis of Fatty Acid Conjugates

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The reagents and the fatty acid–amino acid/peptide conjugates were analyzed using an LC-MS/MS system consisting of an Agilent 1100 LC system (HPLC-DAD-autosampler, Agilent Technologies, Santa Clara, CA, USA) and a QTRAP 6500+ quadruple-linear trap mass spectrophotometer with electrospray ionization (AB Sciex LLC, Framingham, MA, USA). The nuclear magnetic resonance (NMR) analysis was conducted using a Bruker 400 MHz NMR instrument, DMSO-d6 (CAS No. 2206-27-1, 99.9 atom% D, Thermo-scientific, Fair Lawn, NJ, USA) as a solvent, and Topspin 4.3.0 version software. The 1H NMR (400 MHz), 13C NMR (100 MHz), and 13C DEPT data were acquired using a purified compound (30 mg) dissolved in 0.7 mL of DMSO-d6 in a 5 mm diameter NMR tube. DEPT 135 was used to determine the multiplicity of carbon atoms, and CH2 groups showed inverted signals, whereas CH and CH3 groups were upright. The quaternary carbon (C) did not show any signal.
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3

Extraction and Characterization of PSI

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PSI was extracted from organic baby spinach purchased at a local grocery store. Triton X-100 surfactant and 99% p-anisidine (4-methoxyaniline) were purchased from Millipore-Sigma. Silicon (100) wafers were purchased from WRS materials. Chromium-coated tungsten rods were purchased from R.D. Mathis. Gold shot (99.99% purity) was obtained from J&J Materials. Spectra/Por dialysis membrane tubing (6000 to 8000 Da MWCO) was obtained from Repligen. DMSO-d6 (99.5%) was purchased from Thermo Fisher Scientific.
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4

Synthesis and Deposition of ZIF-8 Thin Films

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Zn(NO3)2·6H2O (98%, Sigma-Aldrich), 2-methylimidazole (99%, Sigma-Aldrich), methanol (99.5%, Roth), ethanol (99.8%, Fisher-Scientific), tetrahydrofurane (99.5%, Roth), dimethylformamide (99.8%, Sigma-Aldrich), dimethylsulfoxide (99.9%, Sigma-Aldrich), toluene (99.9%, Roth), para-methyl anisate (98%, Alfa-Aesar), iodobenzene (98%, Alfa-Aesar), sulfuric acid (96%, Roth) and hydrogen peroxide (35%, Roth) were used without further purification. For 1H-NMR measurements, DMSO-d6 (99.8 atom % D, Acros-Organics) and DCl (20 wt% in D2O, 99 atom % D, euriso-top) were used.
As substrates for the deposition of ZIF-8 we used silicon wafers which were cut into 1 × 1 cm pieces and glass slides cut into 2 × 2.5 cm pieces. All substrates were cleaned with ethanol and then immersed in a fresh mixture of sulfuric acid and hydrogen peroxide (2 : 1) for 15 minutes. Subsequently, they were washed with water, ethanol and methanol. Cleaned substrates were not stored but directly used.
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5

Benchmark Solvent and Ionic Liquid Protocols

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DMSO-d6 and substrates including ethanol (99%), propan-1-ol (99%), butan-1-ol (98%), hexan-1-ol (99%), octan-1-ol (99%), benzyl alcohol (99.5%), 4-methylbenzyl alcohol (99%), (4-chlorophenyl)methanol (99.5%), (4-methoxyphenyl)methanol (99.5%), and 4-(hydroxymethyl)phenyl nitrate (99%) were purchased from Acros Organics. Solvents including toluene, diethyl ether, and acetone were purchased from Beijing Chemical Company. DBU, benzylbromide, diphenyl ketone, trioxymethylene, TEMPO, and BHT were purchased from Sigma-Aldrich. H218O [97 atomic % (at %) 18O] was purchased from InnoChem. All the IL, including [EMIM] OAc, [OMIM] OAc, [EMIM] HSO4, [N4,4,4,4] OAc, [BMIM] TFA, [EMIM] BF4, and [EMIM] N(CN)2, were purchased from the Center for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. All ILs were dried in a vacuum at 80°C for 24 hours to remove water or other impurities before use (fig. S17).
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6

Synthesis of Galactarate Derivatives

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Diethyl
2,3:4,5-di-O-isopropylidene-galactarate
>99%, diethyl 2,3:4,5-di-O-methylene-galactarate
>99%, 2,3:4,5-di-O-isopropylidene-galactaric acid
>99%, and 2,3:4,5-di-O-methylene-galactaric acid
>99% were supplied by Royal Cosun. 1,6-Hexamethylenediamine (C6-HMDA)
98%, 1,12-dodecandiamine (C12-DDDA) 98%, dodecanedioic acid (C12)
98%, decanedioic acid (C10) 98%, 1,3-phenylenedimethanamine (MXD)
98%, Irganox 1330, pentafluorophenol-d1 98% (PFP), phenol 99%, dithranol, and NaTFA were purchased from
Sigma-Aldrich and used as supplied. 1,1,1,3,3,3-Hexafluoro-2-propanol
(HFIP), 99.7% DMSO-d6, CDCl3, and D2O were purchased from Acros Organics. Acetone
was purchased from Biosolve.
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7

Synthesis of Fmoc Amino Acid Derivatives

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Fmoc amino acid derivatives were purchased from Anaspec Inc., BACHEM or Chem-Impex Intl. Inc. Diphenyldiazomethane resin and Rink Amide resins were obtained from BACHEM and Novabiochem, respectively. The coupling reagents HBTU and TBTU were purchased from Anaspec Inc. and Novabiochem, respectively. HOBt, piperidine, and reserpine were obtained from Sigma Aldrich. Tetrakis(triphenylphosphine)palladium(0), N-methylaniline, N-methylmorpholine, TIS, and tetrachloro-p-benzoquinone were obtained from Acros. 5-Bromo-7-nitroindoline, thionyl chloride, and Ultramark were acquired from Alfa Aesar. Solvents, DIPEA, TFA, and bromophenol blue were obtained from Fisher Scientific. CDCl3 and DMSO-d6 were purchased from Acros and Cambridge Isotope Laboratories, respectively. Thin layer chromatography was performed on silica gel 60 F254 on aluminum (Merck). Column chromatography was performed on silica gel 60, 230–400 mesh from Natland International Corp.
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8

Analytical Reagents for Chemical Analysis

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Ethanol (96%) was obtained from Brenntag
Schweizerhall AG (Basel, Switzerland). HPLC-grade acetonitrile and
methanol were purchased from Avantor Performance Materials (Radnor
Township, PA, USA). Technical-grade ethyl acetate and n-hexane were from Scharlab S.L. (Barcelona, Spain) and were redistilled
before use. Formic acid was purchased from Scharlab. Ultrapure water
was obtained from a Milli-Q water purification system (Merck Millipore,
Darmstadt, Germany). silica gel 60 F254 coated aluminum TLC plates
and silica gel (0.043–0.063 mm) for flash chromatography were
purchased from Merck KGaA (Darmstadt, Germany). NMR solvents were
from Armar Isotope, Dottingen, Switzerland (methanol-d4, chloroform-d) and Acros Organics,
NJ USA (DMSO-d6).
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9

Synthesis of Fluorinated Amine Derivatives

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2,2-Bis(4-aminophenyl)hexafluoropropane (>98.0%), 4-chlorobenzyl bromide (>95.0%), phenylacetonitrile (>98.0%), sodium hydride (60% dispersion in paraffin liquid), tetrahydrofuran anhydrous (stabilized with 2,6-di-tert-butyl-4-methylphenol, >99.5%), diethyl ether anhydrous (stabilized with 2,6-di-tert-butyl-4-methylphenol, >99.5%), cesium carbonate (>98.0%), iodomethane (>98.5%), and 2,2′-bipyridyl (bpy, >99%) were purchased from Tokyo Chemical Industry Co., Ltd, and used as received. Hydrochloric acid (35.0–37.0%), potassium hydroxide (>86%), sodium chloride (99%), sodium carbonate (>99.8%), sodium thiosulfate (>99.0%), sodium nitrate (>99%), sodium hydrogen carbonate (>99.5%), sodium nitrite (>98.5%), silver nitrate aq. (0.01 M), dimethyl sulfoxide (DMSO, >99%), bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)2, 95%), N,N-dimethylacetamide (>99%), hexane (>96%), dichloromethane (DCM, >99.5%), silica gel N60 (spherical, neutral, 100–210 μm), sodium sulfate (>98.5%), magnesium sulfate, anhydrous (>95.0%), diethyl ether (>99.0%) and lithium aluminum hydride (LAH, >92.0%) were purchased from Kanto Chemical Co., Inc., and used as received. Dimethylsulfoxide-d6 with 0.03% TMS (DMSO-d6, Acros Organics) and chloroform-d1 (CDCl3, Acros Organics) were used as received.
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10

Synthesis of Aromatic Thioethers

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With exception of DMSO and THF all solvents were from Fisher Scientific; DMSO, THF, Et3N, CuI, NH4OAc, propanedinitrile, 4-aminobenzenethiol, and 4-methylbenzenethiol were from Sigma Aldrich. 1-Iodo-2-trifluoromethylbenzene was from Alfa Aesar, K2CO3 was from EM Scientific, CDCl3 was from Cambridge isotope laboratories Inc, and DMSO-d6 and CD3OD were from Acros Organics. The deionized water used was obtained from a Millipore Milli-Q Plus Ultra-Pure Water System.
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