20140324 matthew - naphthenic acids
TRANSCRIPT
![Page 1: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/1.jpg)
Naphthenic acids research
Matthew S. MacLennanChen Lab Group Meeting
March 03, 2014
![Page 2: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/2.jpg)
Outline
• What are Naphthenic acids again?
• What Cai has tried• What I have tried• What I plan to try
![Page 3: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/3.jpg)
Concept of Naphthenic acids
Rogers, V. V; Liber, K.; MacKinnon, M. D. Chemosphere 2002, 48, 519–527.Headley, J. V.; McMartin, D. W. J. Environ. Sci. Heal. Part A 2004, 39, 1989–2010.
![Page 4: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/4.jpg)
Headley, J. V. et al. J. Environ. Sci. Health. A. Tox. Hazard. Subst. Environ. Eng. 2013, 48, 1145–1163.
R = alkyl groupX = COOH, R, OH, Sox, Nox, SHY = C, S, N
Note: ring structures may not befully saturated.
![Page 5: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/5.jpg)
I have forgotten what naphthenic acids were...
• Oil sands process (affected) water (OSPW)• Acidified with H2SO4 to pH 2-2.5• Extracted into organic phase (DCM, EtOAc,
hexanes) and dried to form film• Film reconstituted in solvent of choice for
further preprocessing• = Naphthenic acids fraction compounds
(NAFCs)
![Page 6: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/6.jpg)
What Cai has tried
• Acidify native sample• Extract into EtOAc (dry sample)• Perform NHS-EDC derivatization in DMSO• Inject reaction mixture into CE-MS with 1%
HCOOH/50% MeOH acidic buffer• (PrO)3Si(PEI) coated capillary for EOF
![Page 7: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/7.jpg)
EDC-NHS coupling
R
O
O H
EDC-NHS
R
O
NH
N
CH3
CH3
N
CH3
CH3
NH2
DMSO
OH2
![Page 8: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/8.jpg)
EDC-NHS coupling
http://www.piercenet.com/instructions/2160650.pdf
![Page 9: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/9.jpg)
Sample chromatogram
![Page 10: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/10.jpg)
What I have tried
• Sample induced transient isotachophoresis (tITP) of aqueous derivatized CNLR OSPW (vial 5)
• tITP of aqueous derivatized Syn OSPW (vial 4)
![Page 11: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/11.jpg)
Aqueous EDC-Sulfo-NHS coupling
R
O
O H
EDC, Sulfo-NHS
R
O
NH
N
CH3
CH3
N
CH3
CH3
NH2
buffered H2O, pH ~ 7.5
OH2
![Page 12: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/12.jpg)
Aqueous EDC-Sulfo-NHS coupling
http://www.piercenet.com/instructions/2160650.pdf
![Page 13: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/13.jpg)
Acidified derivatized Syn OSPW
![Page 14: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/14.jpg)
Acidified derivatized Syn OSPW
![Page 15: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/15.jpg)
![Page 16: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/16.jpg)
Scan 505 – Suspect peak
![Page 17: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/17.jpg)
Scan 505; m/z 100-400
![Page 18: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/18.jpg)
Scan 505; m/z 450-700
![Page 19: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/19.jpg)
Scan 505; m/z 700-1000
![Page 20: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/20.jpg)
Acidified derivatized CNLR OSPWtITP injection
![Page 21: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/21.jpg)
![Page 22: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/22.jpg)
Scan 506 – Suspect peak
![Page 23: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/23.jpg)
Scan 506; m/z 150-1400
1093.7 1125.2 1125.9 1138.9 1140.9 1153.5
157.7 169.7 201.7
250.8 268.4 280.0 283.6 290.1 295.8 305.4
536.3 551.3 560.6 575.7 589.5 604.2
804.5 828.5 842.7 856.6 872.0 886.7
![Page 24: 20140324 matthew - naphthenic acids](https://reader035.vdocuments.us/reader035/viewer/2022062306/58f24d0b1a28ab77558b4585/html5/thumbnails/24.jpg)
What I plan to try
• Activation of NAs with NHS or Sulfo-NHS (UV active); Dry-stable
• Fischer esterification with MeOH-HCl; CE-ESI-MS– Commonly used derivatization in lipidomics– Good for fragmentation