See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/325066162 Thesis Presentation: Gold Nanoparticles for Enhanced Laser- Desorption Ionization of Biomolecules Presentation · May 2018 CITATIONS READS 0 96 1 author: Cody Sacks Penn State Hershey Medical Center and Penn State College of Medicine 6 PUBLICATIONS 5 CITATIONS SEE PROFILE Some of the authors of this publication are also working on these related projects: AuNP for LDI-MS of Biomolecules View project All content following this page was uploaded by Cody Sacks on 10 May 2018. The user has requested enhancement of the downloaded file.
Gold Nanoparticles for Enhanced Laser-Desorption Ionization of Biomolecules CODY SACKS, B.S. THE UNIVERSITY OF SCRANTON KATHERINE STUMPO, PH.D. 1
Presentation Overview Background Data Future Research Goals • • Big Picture Optimum M:A ratio • • MALDI-TOF MS Peptides • • Matrices: DHB, AuNP Biomolecules • Steroids 2
MALDI-TOF Mass Spectrometry reflector KE = ½ mv 2 laser detector sample plate ion source reflector flight tube 3
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Big Picture: AuNP vs. DHB as matrix relative abundance Ang III Ang I Sub P ACTH 1-17 mass to charge ratio (m/z) 5
Big Picture: AuNP vs. DHB as matrix Can AuNP improve spectra quality here? Ang I Ang III Sub P ACTH 1-17 Bad DHB range Good DHB range 6
2,5-Dihydroxybenzoic Acid (DHB) Good matrix- transfers energy to analyte well ◦ Conjugated system ◦ Many protons 7
Gold Nanoparticles (AuNP) Applications: ◦ Targeted drug delivery ◦ Tumor detection ◦ Radiation sensitizer https://news.brown.edu/articles/2013/10/nanogold Our research: ◦ LDI-TOF matrix http://file.scirp.org/Html/4-1190177_28878.htm 8
Mass Spectrometry Sample Preparation • DHB • 3:1 acetonitrile:water (0.1% formic acid) @ 5.0 × 10 -1 M • AuNP • 2 nm and 5 nm AuNP obtained from Ted Pella, Inc. • concentrations of 1.5 × 10 14 particles/mL, and 5 × 10 13 particles/mL • Analytes • Dissolved into solvent @ 2.0 × 10 -2 M • Final Solutions • Diluted to M:A of 10 4 :1, 10 5 :1, 10 6 :1 • Diluted to NP:A of 1:10 4 , 1:10 5 , 1:10 6 9
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2 nm AuNP : cholesterol @ 1:10 5 AuNP = 20 Å Citrate layer = Cholesterol layer = 3 Å 71 Å 11
Optimum NP:A Ratio (vs. M/A Ratio) AngI5nm105_0001, AngI5nm1010_0001 Ang I Shimadzu Biotech Axima CFRplus 2.9.3.20110624 %Int. 280 mV 8.8 mV 1318.86 100 90 80 70 60 2nm AuNP 50 1335.14 40 1204.61 30 1416.56 1022.84 1660.33 1159.66 1432.75 20 1301.72 1579.88 1683.71 1004.54 1101.67 1258.55 875.65 10 904.54 1356.99 1946.63 1840.48 1494.40 1612.01 1703.82 0 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 m/z AngI2nm105_0001, AngI2nm1010_0001 Ang I Shimadzu Biotech Axima CFRplus 2.9.3.20110624 %Int. 77 mV 11 mV 1334.70 NP:A 100 90 1318.64 1:10 5 80 70 1:10 10 60 5nm AuNP 50 40 1297.21 30 1341.02 1648.94 20 985.09 1203.17 1301.61 1022.08 800.14 1118.44 943.56 1201.41 1384.68 10 1292.38 1545.73 1827.21 1733.83 1970.22 1636.62 0 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 m/z 12
Biomolecule Library Molecular Weight Compound Name Molecular Formula (g/mol) Structure b-Lactose C12H22O11 340.3 Analyte Formula 2 nm AuNP Observed Species 5 nm AuNP Observed 22 compounds 15 compounds Species Maltose C12H22O11 342.3 -D-Glucose initially after initial [M+Na] + , [M+K] + , [M+2K- a-D Glucose pentacetate C16H22O11 390.34 C 16 H 22 O 11 [M+Na] + , [M+K] + H] + pentacetate Adenine HCl C5H5N5 · HCl · xH2O 135.13 analysis -D-Lactose [M+H] + , [M+Na] + [M+Na] + , F C 12 H 22 O 11 Deoxycholic Adic C24H40O4 392.57 [M+Na] + , [M+2Na-H] + [M+Na] + , [M+2Na-H] + Cholic acid C 24 H 40 O 5 Cholesterol C27H46O 386.65 Cholic Acid C24H40O5 408.57 [M+Na] + , [M+2Na-H] + , [M+Na] + , [M+2Na-H] + Deoxycholic acid C 24 H 40 O 4 [M+K] + Taurocholic Acid C26H45NO7S 515.7058 [M+H] + , [M+Na] + , [M+K] + , [M+H] + , [M+Na] + , [M+K] + , Cholesteryl Acetate C29H48O2 428.69 Diphenhydramine C 17 H 21 NO F + , [F+Au] + [M+Au] + , F + , [F+Au] + Ouabain C29H44O12 584.652 [M+Na] + [M+Na] + Maltose C 12 H 22 O 11 Prednisone C21H26O5 358.428 - 7 molecules for no [M+Na] + [M+Na] + Ouabain C 29 H 44 O 12 Cortisone acetate C21H28O5 402.5 difference in DHB vs. AuNP Proflavine C13H11N3 209.25 Prednisone (cortisone) C 21 H 26 O 5 [M+K] + , [M+Na] + [M+Na] + Diphenhydramine C17H21NO 255.355 [M+2Na-H] + [M+2Na-H] + Taurocholic acid C 26 H 45 NO 7 S ionization or self-ionization D-glucogonic acid C6H12O7 196.16 [M+K] + , [M+Na] + Cholesteryl acetate C 29 H 48 O 2 nd Ibuprofen C13H18O2 206.29 Cortisone acetate C 21 H 28 O 5 [M+K] + nd Propyl Gallate C10H12O5 212.2 [M+Na] + Ibuprofen C 13 H 18 O 2 nd Triethanolamine C6H15NO3 149.19 [M+H] + , [M+Na] + , [M+K] + Propyl gallate C 10 H 12 O 5 nd Glycerophosphate (G3P) C3H9O6P 172.074 Berberine C20H18NO4+ 336.36122 [M+Na] + Cholesterol C 27 H 46 O nd Miconazole C18H14Cl4N2O 416.127 [M+H] + , [M+Na] + Glycerol-3-phosphate C 3 H 9 O 6 P nd Gallic Acid C7H6O5 170.12 13
D-glucoronic acid: no significant difference (A)DHB 10 6 :1 (B)5 nm AuNP 1:10 5 14
Berberine: self-ionizing molecule 15
Cholesterol (A) DHB 10 6 :1 (B) 5 nm AuNP 1:10 6 16
Lactose (A) DHB 10 6 :1 (B) 5 nm AuNP 1:10 5 17
Diphenhydramine (A) 2 nm AuNP 1:10 5 (B) 5 nm AuNP 1:10 5 18
Deoxycholic acid (A) DHB 10 6 :1 (B) 2 nm AuNP 1:10 4 [M-H+2Na] + 19
Cholic acid (ChA), Deoxycholic acid (dChA), and Taurocholic acid (TChA). (A) DHB 10 5 :1 (B) 5 nm AuNP 1:10 6 20
Cholic acid (ChA), Deoxycholic acid (DChA), and Taurocholic acid (TChA) 2 nm AuNP 1:10 5 DChA/ DChA/ 21
Cholic acid, negative ion mode (A) DHB 10 4 :1 (B)2 nm AuNP 1:10 5 22
Future Goals SHORT TERM LONG-TERM Understand the fragmentation mechanism of Selective ionization steroids Develop a library of molecule ionization patterns 23 View publication stats View publication stats
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