A Dual Ligand Sol–Gel Organic-Silica Hybrid Monolithic Capillary for In-Tube SPME-MS/MS to Determine Amino Acids in Plasma Samples
Abstract
:1. Introduction
2. Results
2.1. Hybrid Monolithic Capillary Synthesis
2.2. Characterization of Hybrid Silica Monoliths
2.3. In-Tube SPME-MS/MS Optimization
2.4. Adsorption Experiments
2.5. In-Tube SPME-MS/MS Analytical Validation
2.6. Comparison of the Proposed Method with Literature Methods
3. Materials and Methods
3.1. Standards and Reagents
3.2. Synthesis of Hybrid Silica-Based Monolithic Capillaries Bearing Amino and Cyano Groups
3.3. Hybrid Silica Monolithic Capillary Characterization
3.4. Plasma Samples
3.5. MS/MS Conditions
3.6. In-Tube SPME Procedure
3.7. Adsorption Capacity
3.8. Analytical Validation
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
Procedure | TEOS (µL) | APTES (µL) | CN-TEOS (µL) | H2O/EtOH (µL) | TEOS/APTES/CN-TEOS (µL) | Aging Temperature (°C) |
---|---|---|---|---|---|---|
1 | 56 | 28 | 28 | 100:20 | 2:1:1 | 60 |
2 | 38 | 38 | 38 | 100:20 | 1:1:1 | 60 |
3 | 56 | 56 | 0 | 100:20 | 1:1:0 | 60 |
4 | 56 | 0 | 56 | 100:20 | 1:0:1 | 60 |
5 | 56 | 28 | 28 | 50:50 | 2:1:1 | 60 |
6 | 56 | 28 | 28 | 50:50 | 2:1:1 | 22 |
Analyte | Precursor Ion | Product Ion (Quantification) | DP (V) | CE (V) | Product Ion (Identification) |
---|---|---|---|---|---|
Tryptophan | 205.2 | 146.0 | 20 | 12 | 188.1 |
Methionine | 150.0 | 56.0 | 20 | 15 | 104.0 |
Methionine d3 | 153.1 | 56.0 | 20 | 15 | 107.1 |
Tyrosine | 182.1 | 136.1 | 25 | 15 | 90.8 |
Leucine/Isoleucine | 132.1 | 86.0 | 20 | 10 | 44.0 |
GABA | 104.1 | 87.0 | 30 | 15 | 45.0 |
Serotonin | 177.1 | 115.1 | 20 | 36 | 104.9 |
Glutamic acid | 148.1 | 84.0 | 25 | 15 | 102.1 |
Lysine | 147.2 | 88.0 | 25 | 15 | 107.0 |
Aspartic acid | 134.1 | 74.0 | 20 | 12 | 88.0 |
Serine | 106.0 | 60.0 | 20 | 10 | 88.0 |
Alanine | 90.0 | 44.0 | 20 | 10 | 62.0 |
Alanine 13C315N | 94.2 | 47.1 | 20 | 10 | 64.8 |
MOBILE PHASE A: Water B: Acetonitrile | ||||
---|---|---|---|---|
Time (min) | % A | % B | Valve Position | Comments |
0.0 | 0 | 100 | 1 | pre-concentration of analytes and exclusion of plasma macromolecules |
2.0 | 100 | 0 | 2 | Elution of analytes from monolithic capillary to mass spectrometer |
4.0 | 100 | 0 | 2 | Post capillary infusion of acetonitrile with 0.1% formic acid |
7.0 | 100 | 0 | 1 | Final elution step and start of gradient elution to clean up the capillary column |
Validation Parameters | Ala | Leu/Iso | Met | Ty | Try | Ser | Glu | Lys | Asp |
---|---|---|---|---|---|---|---|---|---|
Linearity (R2) | 0.995 | 0.993 | 0.998 | 0.995 | 0.997 | 0.990 | 0.996 | 0.991 | 0.993 |
Slope Intercept | 0.0013 0.4277 | 0.0110 2.4736 | 0.0704 0.6808 | 0.0057 0.1844 | 0.0251 0.6792 | 0.0024 0.3963 | 0.0022 0.0746 | 0.0046 0.0859 | 0.0057 0.0092 |
LOF (p-value) | 0.997 | 0.803 | 0.489 | 0.251 | 0.876 | 0.892 | 0.972 | 0.251 | 0.875 |
Linear range (nmol mL−1) | 45–360 | 15–300 | 12–102 | 10–102 | 9–96 | 12–210 | 12–90 | 12–102 | 6–36 |
Student’s t-test (p-value) | 0.520 | 0.087 | 0.125 | 0.907 | 0.079 | 0.077 | 0.219 | 0.280 | 0.244 |
Plasma Concentration (nmol mL−1) | Ala | Leu/Iso | Met | Ty | Try | Ser | Glu | Lys | Asp |
---|---|---|---|---|---|---|---|---|---|
Average values | 270.8 ± 60.1 | 246.1 ± 28.0 | 18.3 ± 5.1 | 40.5 ± 10.4 | 37.1 ± 9.7 | 143.0 ± 48.6 | 31.8 ± 11.2 | 20.6 ± 4.0 | 11.2 ± 7.5 |
Analytes | Sample Preparation | Sample Volume (µL) | Analytical Method | Elution of Analytes (min) | validation Parameters (Intra and Inter Assays) | Ref. |
---|---|---|---|---|---|---|
10 amino acids | Protein precipitation | Plasma 50 | UHPLC-MS/MS-Ascentis® Express HILIC column (4.6 × 100 mm, 2.7 µm). MP: A = Ammonium acetate solution 10 mM; B = acetonitrile with 0.1% FA | 3.2 | LLOQ: 9.7–13.3 nmol mL−1 Precision: 2–10% (CV) Accuracy: −2.1–9.9% (RSE) | [9] |
33 Amino acids | Protein precipitation | Plasma 100 | Two columns: 1 - PGC column (Thermo Fisher Scientific, 3 µm Hypercarb, 4.6 mm i.d. × 50 mm), and 2 - fused-core column (Advanced Materials Technology, 2.7 µm Halo C18, 2.1 mm i.d. × 100 mm) | 9.4 | LLOQ: 0.1–10.0 nmol mL−1 Precision: 1.2–9.2% (CV) Accuracy: N.A | [63] |
20 amino acids | Protein precipitation | Serum 100 | UHPLC-MS/MS CROWNPAK CR-I(+) column (3.0-mm i.d. × 150 mm, 5 μm) | 10.1 | LLOQ: 0.1–10.0 nmol mL−1 Precision: 2.6–10.1% (CV) Accuracy: −12.8–12.4% (RSE) | [62] |
22 amino acids | Protein precipitation | Plasma 10 | HPLC-MS/MS Two Agilent Zorbax SB-C18 columns, (2.1 mm × 50 mm, 1.8 µm) | 35.0 | LLOQ: 0.01–0.07 nmol mL−1 Precision: 1.0–15.0% (CV) Accuracy: −12.8–12.4% | [64] |
10 amino acids | In-tube SPME | Plasma 200 | In-tube SPME-MS/MS with post capillary infusion | 5.2 | LLOQ: 6–45 nmol mL−1 Precision: 1.1–19.0% (CV) Accuracy: −14.4–19.6% (RSE) | This work |
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Miranda, L.F.C.; Gonçalves, R.R.; C. Queiroz, M.E. A Dual Ligand Sol–Gel Organic-Silica Hybrid Monolithic Capillary for In-Tube SPME-MS/MS to Determine Amino Acids in Plasma Samples. Molecules 2019, 24, 1658. https://doi.org/10.3390/molecules24091658
Miranda LFC, Gonçalves RR, C. Queiroz ME. A Dual Ligand Sol–Gel Organic-Silica Hybrid Monolithic Capillary for In-Tube SPME-MS/MS to Determine Amino Acids in Plasma Samples. Molecules. 2019; 24(9):1658. https://doi.org/10.3390/molecules24091658
Chicago/Turabian StyleMiranda, Luis F. C., Rogéria R. Gonçalves, and Maria E. C. Queiroz. 2019. "A Dual Ligand Sol–Gel Organic-Silica Hybrid Monolithic Capillary for In-Tube SPME-MS/MS to Determine Amino Acids in Plasma Samples" Molecules 24, no. 9: 1658. https://doi.org/10.3390/molecules24091658