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7 protocols using cyclohexanone

1

Synthesis and Characterization of Silica-based Materials

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PdCl2 (Silversalt, St. Petersburg, Russia, 98%), LiCl (TTX, Sergiev Posad, Russia, 98+), isopropanol (IPA, 99.5+%, Acros, Fair Lawn, NJ, USA), tetramethylorthosilicate (TMOS, Acros, 99%), (3-aminopropyl)trimethoxysilane (APTMS, Acros, 95%), N-(2-aminoethyl)-3-(trimethoxysilyl)propylamine (AEAPTMS, Sigma-Aldrich, St. Louis, MO, USA, 97%), (S)-(+)-2-phenylglycine methyl ester hydrochloride (Acros, 97%), L-phenylalanine methyl ester hydrochloride (Acros, 98%), methanol (Acros, 99.9%), hexene-1 (Acros, 97%), benzene (Sigma-Aldrich, 99.8%), acetophenone (Acros, 98%), benzaldehyde (Acros, 98+%), benzophenone (Acros, 99%), hexyne-1 (Acros, 98%), dicyclopentadiene (Merck, Darmstadt, Germany, 98%), cyclohexanone (Acros, 99.8%) and 1,4–dioxane (Acros, 99+%) were used without further purification. Lithium tetrachloropalladate (II) was prepared by mixing 1 mol of PdCl2 and 2 mol of LiCl in methanol and stirring for 24 h at room temperature.
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2

Synthesis and Characterization of Silica-Based Catalysts

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All manipulations were carried out under air. Distilled water was used directly from a Milli-Q purification system (Millipore, Burlington, MA, USA). Acetonitrile, ethanol, methanol (synthesis grade, Aldrich) were used as solvents as received. Tetraethyl orthosilicate (TEOS, 98% Aldrich, St. Louis, MI, USA), ammonium hydroxide solution (25%, Aldrich), 3-(Triethoxysilyl)propionitrile (97%, Aldrich), cis-cyclooctene (95%, Alfa Aesar, Karlsruhe, Germany), cyclooctene oxide (99%, Aldrich), cyclohexene (99%, Acros), cyclohexene oxide (98%, Aldrich), 2-cyclohexen-1-ol (95%, TCI, Tokyo, Japan)), 2-cyclohexen-1-one (96%,TCI), cis-1,2-cyclohexanediol (99%, Acros, Geel, Belgium), cyclohexanol (99%, Alfa Aesar), cyclohexanone (99.8%, Acros) and TBHP (70% in water, Aldrich) were used as received.
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3

Synthesis and Catalytic Evaluation of Cyclic Compounds

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All manipulations were carried out under air. Distilled water was used directly from a Milli-Q purification system (Millipore, Burlington, MA, USA). Acetonitrile, ethanol, methanol and diethyl ether (synthesis grade, Aldrich, St. Louis, MI, USA) were used as solvents and employed as received. Tetraethyl orthosilicate (TEOS, 98% Aldrich), ammonium hydroxide solution (25%, Aldrich), 3-aminopropyltriethoxysilane (APTES, 99%, Aldrich), cis-cyclooctene (CO, 95%, Alfa Aesar, Ward Hill, MA, USA), cyclooctene oxide (COE, 99%, Aldrich), cyclohexene (CH, 99%, Acros, Geel, Belgium), cyclohexene oxide (CHO, 98%, Aldrich), 2-cyclohexen-1-ol (CHol, 95%, TCI, Tokyo, Japan), 2-cyclohexen-1-one (CHone, 96%, TCI), cis-1,2-cyclohexanediol (CHD, 99%, Acros), limonene (Lim, 98%, Aldrich), limonene oxide (LO cis/trans mixture, 97%, Aldrich), (1S, 2S, 4R)-(+)-limonene-1,2-diol (ax-LD, 97%, Aldrich), L-carveol (Colcis/trans mixture, 95%, Aldrich), (R)-(-) Carvone (Cone 98%, Aldrich), cyclohexanol (CYol, 99%, Alfa Aesar, Karlsruhe, Germany), cyclohexanone (CYone, 99.8%, Acros), phosphotungstic acid hydrate (reagent grade, Aldrich), molybdatophosphoric acid hydrate (reagent grade, Merck, Darmstadt, Germany) and TBHP (70% in water, Aldrich) were used as received. The pure cis-LO, trans-LO and eq-LD were synthesized according to literature procedures [58 (link),59 (link),60 (link)].
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4

PDMS Microfluidic Device Fabrication

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Microfluidic devices were fabricated in polydimethylsiloxane (PDMS) using the standard soft lithography process with dry photoresist masters, as we detailed previously [31 (link)]. Briefly, 3″ silicon wafers were dehydrated for 15 min on a 225 °C hotplate, laminated with a 50 μm thick ADEX film (DJ Microlaminates Inc., Sudbury, MA, USA) and baked for 5 min on a 65 °C hotplate. Next, the wafers were exposed to UV light (I-line 365 nm, Optical Associates Inc., San Jose, CA, USA) for 33 s at 10 mW/cm2 through a mask plate in hard contact. The wafers were developed in cyclohexanone (98%, Acros Organics, Pittsburg, PA, USA), washed with isopropyl alcohol (IPA) and deionized (DI) water, air dried and baked for 90 min on a 170 °C hotplate. A mixture of a 10:1 ratio of PDMS (Sylgard 184, Dow Corning, Midland, MI, USA) and curing agent was cast on the master, degassed for 90 min in a vacuum oven and cured for 120 min at 80 °C. Devices were cut out using a scalpel and inlet and outlet ports were cored using a biopsy punch with a diameter of 1.5 mm. Finally, devices were bonded to standard microscope glass slides using an oxygen plasma treatment at 10 W for 20 s (PE-50, Plasma Etch Inc., Carson City, NV, USA), baked for 60 min at 80 °C and allowed to cool to room temperature before use.
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5

Synthesis and Characterization of PDLLA-PVA Polymers

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Throughout the experiments, poly(d,l-lactic acid) (PDLLA), Mn 47,000 gmol−1, from Evonik Rohm GmbH (Darmstadt, Germany), poly(vinyl acetate-co-alcohol) (PVA) Mw 25 kDa, 88% hydrolysed from Sigma-Aldrich (St. Louis, MO, USA,)and ethyl acetate from Fisher Scientific (Waltham, MA, USA) were used, without modification.
Surfmers were produced in house using poly(ethylene glycol) methyl ether methacrylate (mPEGMA), Mn = 300, ethylene glycol phenyl ether acrylate (EGPEA), tetrahydrofurfuryl acrylate (THFuA), and 2,2′-azobis (2-methylpropionitrile) (AIBN, 98%). These materials were purchased from Sigma Aldrich and used without further purifications. The catalytic CTA, bis[(difluoroboryl)diphenylglyoximato] cobalt (II) (PhCoBF) (DuPont, DE, USA). Cyclohexanone and heptane used as solvents for the synthesis and precipitations, respectively, were used as received and supplied by Fisher Scientific.
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6

Preparation of Cationic Lignin Nanoparticles

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Never-dried softwood kraft pulp fibers (Metsä Board Husum mill, Sweden) were used to prepare TCNF following the method of (Saito et al. 2007 (link)). Sulfur-free birch lignin produced by BLN process (named after the company that initially developed the technology) was provided by CH Bioforce Oy (Finland). Briefly, the process involves hot water (150 °C) extraction of hemicelluloses from biomass followed by alkali cooking to extract lignin, all in oxygen-starved conditions (von Schoultz 2015 ). The LNPs were prepared by anti-solvent nanoprecipitation in acetone and water (Figueiredo et al. 2021 (link)). These LNPS were cationized by coating with glycidyltrimethylammonium chloride (GTAC)-treated lignin to produce cationic LNPs (cLNPs) (Agustin et al. 2022 (link); Sipponen et al. 2017 (link)). The detailed preparation of TCNF, LNPs, and cLNPs and their basic characteristics are available in the Supporting Information (Fig. S2). Hexadecane, GTAC, cyclohexanone, and acetone were purchased from Fisher Scientific (Finland). The pharmaceutical compounds, which are certified reference materials, dialysis membrane tubing (Spectra/Por 7, 6–8 kDa molecular weight cut-off (MWCO), Spectra/Por 1, 1 kDa MWCO), glass microfibre filters with a 0.7 µm pore size (Whatman GF/F), chromasolv-grade acetonitrile and methanol were obtained from Sigma-Aldrich (Finland).
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7

Preparing Black Phosphorus in Inert Atmosphere

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All solvents were purchased from Sigma Aldrich unless otherwise noted. The solvents were degassed prior to use and handled under nitrogen. Black phosphorus (smart elements, ~99.998%), red phosphorus (Sigma Aldrich, ≥ 99.999+%), N-methyl-2-pyrrolidone (Sigma Aldrich or Acros Organics, anhydrous, 99.5%) 2-propanol (FisherSci, electronic grade), cyclopentanone (≥ 99%), 1-cyclohexyl-2-pyrrolidone (≥ 99%), 1-dodecyl-2-pyrrolidinone (≥ 99%), benzyl benzoate (≥ 99.0%), 1-octyl-2-pyrrolidone (≥ 98%), 1-vinyl-2-pyrrolidinone (≥ 99%), benzyl ether (≥ 98%), 1,3-dimethyl-2-imidazolidinone (≥ 99%), cyclohexanone (≥ 99.8%), chlorobenzene (≥ 99.5%), dimethylsulfoxide (≥ 99.9%), benzonitrile (anhydrous, ≥ 99%), Nmethylformamide (≥ 99%), dimethylformamide (≥ 99%), benzaldehyde (≥ 99%).
All samples were prepared in a nitrogen-filled glove box (O2 < 1 ppm) and transferred from instrument to instrument using custom-designed glassware with Rotaflo stopcocks. When necessary, instrument loading chambers and/or the entire instrument was enclosed in N2-filled glove bags to provide an inert atmosphere.
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