Exp099

Researcher
David Bulger

Objective
Determine the solubility of [|4-pyrenebutanoic acid] in [|DMF] and [|DMSO].

Procedure
Make saturated solutions of 4-pyrenebutanoic acid in DMF and DMSO and determine solubility using SAMS and internal standard (IS) methods.

Pictures
[|ONSC099-1] [|ONSC099-2] [|ONSC099-3] [|ONSC099-4] [|ONSC099-5] [|ONSC099-6] [|ONSC099-7]

Spectra
[|ONSC099-1] [|ONSC099-2] [|Raw JCAMP-DX file for ONSC099-1] [|Raw JCAMP-DX file for ONSC099-2]

Spreadsheet
[|ONSC099-1] [|ONSC099-2] media type="googlespreadsheet" key="rcbIGD9ZlnB-xpD3Be_nGuA" height="400" width="900"

Solubilities

 * Spectrum || Solute Signal Used || Solvent Signal Used || Method || Solvent || Solubility (__M__) ||
 * [|ONSC099-1] || 2nd Methylene || Dimethyl || SAMS || DMF || 1.86 ||
 * [|ONSC099-1] || 1st Methylene || Dimethyl || SAMS || DMF || 1.90 ||
 * [|ONSC099-1] || Last Aromatic Proton || Dimethyl || SAMS || DMF || 1.87 ||
 * [|ONSC099-1] || 2nd Aromatic Proton || Dimethyl || SAMS || DMF || 1.65 ||
 * [|ONSC099-1] || 2nd Methylene || Aldehyde || SAMS || DMF || 2.45 ||
 * [|ONSC099-1] || 1st Methylene || Aldehyde || SAMS || DMF || 2.50 ||
 * [|ONSC099-1] || Last Aromatic Proton || Aldehyde || SAMS || DMF || 2.47 ||
 * [|ONSC099-1] || 2nd Aromatic Proton || Aldehyde || SAMS || DMF || 2.23 ||
 * [|ONSC099-2] || 2nd Methylene || Dimethyl || SAMS || DMSO || 2.16 ||
 * [|ONSC099-2] || 1st Methylene || Dimethyl || SAMS || DMSO || 2.16 ||
 * [|ONSC099-2] || Last Aromatic Proton || Dimethyl || SAMS || DMSO || 2.09 ||
 * [|ONSC099-2] || 2nd Aromatic Proton || Dimethyl || SAMS || DMSO || 2.00 ||
 * ONSCEXP061 || 2nd Methylene || Dimethyl || SAMS || DMSO || 2.13 ||
 * Spectrum || Solute Signal Used || Internal Standard || Solvent || Solubility (__M__) ||
 * [|ONSC099-1] || 2nd Methylene || 1,2-dichloroethane || DMF || 2.48 ||
 * [|ONSC099-1] || 1st Methylene || 1,2-dichloroethane || DMF || 2.58 ||
 * [|ONSC099-1] || Last Aromatic Proton || 1,2-dichloroethane || DMF || 2.52 ||
 * [|ONSC099-1] || 2nd Aromatic Proton || 1,2-dichloroethane || DMF || 2.04 ||
 * [|ONSC099-2] || 2nd Methylene || 1,2-dichloroethane || DMSO || 3.28 ||
 * [|ONSC099-2] || 1st Methylene || 1,2-dichloroethane || DMSO || 3.27 ||
 * [|ONSC099-2] || Last Aromatic Proton || 1,2-dichloroethane || DMSO || 3.07 ||
 * [|ONSC099-2] || 2nd Aromatic Proton || 1,2-dichloroethane || DMSO || 2.84 ||
 * ONSCEXP051 || 2nd Methylene || acetonitrile || DMSO || 1.91 ||
 * [Excellent demonstration of the importance of checking multiple protons with SAMS. Can you provide reasons for preferring one or a few measurements over the others, or would an average be the best measurement the technique can provide? --BH]** From what Dr. Bradley has told me, the best measurement first of all does not have any overlapping peaks. In general, methylene singals tend to give better measurements than aromatic or carboxylic acid signals.

Note: Internal Standard signal was not of the highest quality and the IS measurements may be disregarded.

Discussion
Out of all the different solubility measurements, the 2nd methylene signal of the solute and the dimethyl signal of DMF yielded the best peaks. Therefore, those peaks were used to determine the solubility of 4-pyrenebutanoic acid in DMF and DMSO, which was found to be 1.86 __M__ and 2.16 __M__ respectively using the SAMS method. In ONSCEXP061, the solubility in DMSO was found to be 2.13 __M__ using SAMS, which is consistent with the results in this experiment. The IS method could not be used properly, since the 1,2-dichloroethane signal was distorted. However, ONSCEXP051 found the solubility in DMSO using an acetonitrile internal standard to be 1.91 __M__, which is slightly less than was found in this experiment by SAMS. Overall, the solubility of 4-pyrenebutanoic acid in DMSO is most likely around 1.9-2.2 __M__ and in DMF around 1.6-1.9 __M__.

Conclusion
Overall, the solubility of 4-pyrenebutanoic acid is estimated to be around 1.9-2.2 __M__ in DMSO and around 1.6-1.9 __M__ in DMF.

Log
16:44 Labeled half-dram vials for DMF (ONSC099-1) and DMSO (ONSC099-2) and weighed 16:47 Added 300 uL of each solvent and weighed 16:51 Added 4-pyrenebutanoic acid, weighed, and vortexed for 10 sec - solid went into solution 17:01 Added 4-pyrenebutanoic acid, weighed, and vortexed for 10 sec 17:11 Photo ([|ONSC099-1]) 17:15 Began sonication (25 degrees Celsius) 17:20 Weighed vials 17:23 Prepared NMR tubes (cleaning, drying, cooling) 17:43 Finished sonication (32 degrees Celsius) 17:47 Photo ([|ONSC099-2]) 17:50 Weighed 17:51 Centrifuged for 3 min 17:55 Photo ([|ONSC099-3]) 17:56 Transferred supernatant to corresponding half-dram vials 1A and 2A using Pasteur pipet 17:59 Centrifuged for 3 min 18:07 Photo (__ ONSC099-4 __) 18:08 Transferred supernatant to corresponding half-dram vials 1B and 2B using Pasteur pipet 18:11 Centrifuged for 3 min 18:17 Photo ([|ONSC099-5]) 18:18 Added 700 uL of DMSO-d6 to half-dram vials N1 and N2 18:26 Added 10 uL of 1,2-dichloroethane to N1 and N2 18:30 Added 100 uL of 1B and 2B to corresponding N1 and N2 by inserting the pipet tip beneath the surface of the solution when dispensing contents in order to prevent evaporation and vortexed for 10 sec 18:36 Placed in water bath (24.5 degrees Celsius) 18:39 Photo ([|ONSC099-6]) 18:42 Labeled NMR tubes (ONSC099-1 and ONSC099-2) 18:43 Water bath temperature at 23.5 degrees Celsius 18:57 Water bath temperature at 22.8 degrees Celsius 18:58 Removed from water bath 19:00 Vortexed for 30 sec 19:01 Transferred contents of N1 and N2 to corresponding NMR tubes (ONSC099-1 and ONSC099-2) and parafilmed 19:05 Photo ([|ONSC099-7]) 19:30 Collected 500 MHz NMR spectrum ([|ONSC099-1]) 19:45 Collected 500 MHz NMR spectrum ([|ONSC099-2])
 * Vial || Mass (g) ||
 * ONSC099-1 || 2.404 1 ||
 * ONSC099-2 || 2.397 7 ||
 * Vials || Mass (g) ||
 * ONSC099-1 || 2.721 8 ||
 * ONSC099-2 || 2.775 8 ||
 * Vials || Mass (g) ||
 * ONSC099-1 || 2.908 7 ||
 * ONSC099-2 || 2.993 7 ||
 * Vials || Mass (g) ||
 * ONSC099-1 || 3.008 7 ||
 * ONSC099-2 || 3.206 7 ||
 * Vials || Mass (g) ||
 * 1N || 2.419 5 ||
 * 2N || 2.400 2 ||
 * Vials || Mass (g) ||
 * ONSC099-1 || 3.009 1 ||
 * ONSC099-2 || 3.207 2 ||
 * Vials || Mass (g) ||
 * N1 || 3.278 4 ||
 * N2 || 3.255 7 ||
 * Vials || Mass (g) ||
 * N1 || 3.291 9 ||
 * N2 || 3.268 8 ||
 * Vials || Mass (g) ||
 * N1 || 3.398 1 ||
 * N2 || 3.378 1 ||