Simultaneous Determination of Tobacco Smoke Exposure and Stress Biomarkers in Saliva Using In-Tube SPME and LC-MS/MS for the Analysis of the Association between Passive Smoking and Stress
Abstract
:1. Introduction
Biomarker 1 | Analytical Method 2 | Linearity Range (ng mL–1) | LOD (pg mL–1) | LOQ (pg mL–1) | Precision RSD (%) | Recovery (%) | Remarks | Ref. |
---|---|---|---|---|---|---|---|---|
Nic, Cot, OH-Cot | SPE GC–MS/MS | 0.5–1000 | 500 | 500 | 1.56–9.62 | 89–92 | Oral fluid 0.2 mL, derivatization | [48] |
Nic, Cot | HPLC–UV | Saliva 5 mL | [49] | |||||
Nic, Cot, alkaloids | IT-SPME LC–MS | 0.5–20 | 15–40 | - | 0.53–4.73 | 83–98 | Saliva 0.1–0.2 mL | [50] |
Nic, Cot, alkaloids | SPE LC–MS/MS | 1–100 | 250–1000 | 1000 | ≤10 | 80–119 | Oral fluid 0.5 mL | [51] |
CRT | Immuno FET sensor | 0.01–15 | 5 | ≤10 | 104 | Saliva 0.05 mL | [55] | |
CRT, CRN | SPE HPLC–UV | 2.0–40 | 36–72 | 2.7–7.0 | 88–99 | Saliva 0.05 mL | [57] | |
CRT, CRN | IL-DDDME LC–UV/Vis | 5–500 | 110–160 | 370–540 | 2.8–5.5 | 83–116 | Saliva 1–1.5 mL | [58] |
CRT, CRN, corticosterone | MEPS-HPLC–DAD | 5–100 | 1500 | 5000 | 2.6–4.9 | 82–86 | Saliva 0.4 mL | [59] |
CRT, CRN, MEL | TF LC–MS/MS | 0.2–10 0.001–0.1 (MEL) | - | 200–1900 1.4 (MEL) | ≤5 | 95–106 | Saliva 0.05 mL | [60] |
CRT, TES, DHEA | IT-SPME LC–MS | 0.002–100 | 0.3–8.9 | 10–290 | 1.0–4.9 | 94–106 | Saliva 0.1 mL | [67] |
CRT, DHEA-S | LC–MS/MS | 1.0–25.0 | 20–30 | 30–60 | 4.6–17.9 | 95–110 | Saliva 0.4 mL | [61] |
CRT, CRN | SPE UPLC–MS/MS | 0.005–10 | 5 | 10–50 | 2–4 | 95–103 | Saliva 0.2 mL | [62] |
CRT, other steroids | SPE UPLC–MS/MS | 0.005–5.0 | - | 50 (CRT) | 7.2 (CRT) | - | Saliva 0.2 mL | [63] |
CRT, TES, DHEA, DHEA-S | IT-SPME LC–MS | 0.01–20 | 0.40–8.5 | 36–768 | 0.9–6.1 | 95–106 | Saliva 0.05 mL | [20] |
CRT, CRN, MEL | LLE UPLC–MS/MS | 0.2–10 0.001–0.1 (MEL) | 36–54 0.7 (MEL) | 181–360 2.3(MEL) | 7–14 | 86–99 | Saliva 0.25 mL | [64] |
Nic, Cot, CRT, DA, 5-HT, MEL, OXT | IT-SPME LC–MS | 0.01–25 | 0.12–3.7 | 4–124 | 1.3–7.9 | 82–107 | Saliva 0.05 mL | This study |
2. Results and Discussion
2.1. Optimization of IT-SPME and Desorption of Biomarkers
2.2. LC–MS/MS Analysis of Biomarkers
2.3. Validation of the Developed IT-SPME LC–MS/MS Method
2.4. Analysis of Saliva Samples
2.5. Analysis of the Relationship between Stress and Tobacco Smoke Exposure by Measurements of Salivary Biomarkers and HRV
3. Materials and Methods
3.1. Reagents and Materials
3.2. Sampling, Preparation and Analysis of Saliva Samples
3.3. LC–MS/MS Conditions
3.4. IT-SPME Procedure and On-Line Coupling with LC–MS/MS
3.5. Method Validation Study
3.6. HRV Analysis by Fingertip Pulse Wave Measurement
3.7. Tobacco Smoke Exposure Assessment by Biomarker and HRV Analyses
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Biomarker | Linearity | LOD 2 (pg mL−1) | LOQ 3 (pg mL−1) | ||
---|---|---|---|---|---|
Range (ng mL−1) | CC 1 | Direct Injection | IT-SPME | IT-SPME | |
Nic | 0.05–2.5 | 0.9977 | 7.0 | 0.22 | 7.7 |
Cot | 0.01–0.5 | 0.9999 | 2.6 | 0.12 | 4.0 |
CRT | 0.2–10 | 0.9997 | 23 | 0.78 | 27 |
5-HT | 0.02–1.0 | 1.0000 | 18 | 0.39 | 13 |
MEL | 0.01–0.5 | 0.9994 | 24 | 0.45 | 16 |
DA | 0.2–10 | 0.9993 | 31 | 1.4 | 48 |
OXT | 0.5–25 | 0.9998 | 138 | 3.7 | 124 |
Compound | Concentration (ng mL−1) | Precision (RSD 1 %), (n = 5) | |
---|---|---|---|
Intra–Day | Inter–Day | ||
Nic | 0.25 | 5.7 | 9.5 |
1 | 5.9 | 9.9 | |
2.5 | 5.8 | 9.4 | |
Cot | 0.05 | 3.4 | 7.3 |
0.2 | 6.8 | 13.5 | |
0.5 | 3.2 | 5.0 | |
CRT | 1 | 6.1 | 6.7 |
4 | 2.6 | 6.8 | |
10 | 1.6 | 3.8 | |
5-HT | 0.5 | 6.7 | 14.6 |
2 | 3.0 | 5.7 | |
5 | 1.9 | 2.8 | |
MEL | 0.05 | 4.8 | 5.5 |
0.2 | 3.0 | 2.3 | |
0.5 | 1.3 | 2.2 | |
DA | 1 | 5.0 | 7.8 |
4 | 3.9 | 4.7 | |
10 | 3.4 | 2.9 | |
OXT | 2.5 | 7.9 | 8.0 |
10 | 3.7 | 4.0 | |
25 | 3.6 | 3.7 |
Compound | Spiked (ng mL−1 Saliva) (ng mL−1 Saliva) | Recovery ± SD (%), (n = 3) (n = 3) |
---|---|---|
Nic | 2.5 | 105.4 ± 2.5 |
10 | 96.8 ± 0.6 | |
25 | 98.2 ± 0.9 | |
Cot | 0.5 | 105.4 ± 4.0 |
2 | 99.1 ± 0.7 | |
5 | 100.4 ± 0.4 | |
CRT | 10 | 99.1 ± 1.4 |
40 | 97.9 ± 4.4 | |
100 | 101.0 ± 1.2 | |
5-HT | 5 | 98.2 ± 2.2 |
20 | 98.9 ± 1.5 | |
50 | 99.2 ± 2.6 | |
MEL | 0.5 | 96.9 ± 0.5 |
2 | 96.2 ± 0.7 | |
5 | 102.9 ± 5.9 | |
DA | 10 | 82.3 ± 2.6 |
40 | 96.7 ± 3.9 | |
100 | 82.1 ± 1.2 | |
OXT | 25 | 93.1 ± 3.7 |
100 | 106.6 ± 1.1 | |
250 | 93.8 ± 2.5 |
Content 1 (pg mL−1 Saliva) | HRV Indicator | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
Nic | Cot | CRT | 5-HT | MEL | DA | OXT | SDNN 3 | Ln LF/Ln HF 4 | Ln TP 5 | |
Max. | 807 | 54 | 732 | 3706 | <LOQ 2 | 224 | 691 | 88 | 1.7 | 9.1 |
Med. | 377 | 12 | 482 | 164 | <LOQ | 44 | 114 | 47 | 0.9 | 6.6 |
Min. | 207 | 4 | 220 | 23 | <LOQ | <LOQ | <LOQ | 19 | 0.7 | 3.8 |
Ave. | 395 | 18 | 497 | 457 | <LOQ | 64 | 178 | 47 | 1.0 | 6.4 |
SD | 153 | 12 | 134 | 792 | – | 46 | 162 | 15 | 0.2 | 1.2 |
Compound | Mass Transition (m/z) | DP 1 (V) | EP 2 (V) | CE 3 (V) | CXP 4 (V) |
---|---|---|---|---|---|
Nicotine (Nic) | 163.1 → 132.1 | 70 | 10 | 20 | 10 |
Cotinine (Cot) | 177.1 → 80.2 | 75 | 10 | 30 | 15 |
Cortisol (CRT) | 363.0 → 120.9 | 70 | 10 | 30 | 10 |
Serotonin (5-HT) | 177.2 → 160.2 | 25 | 5 | 15 | 3 |
Melatonin (MEL) | 233.1 → 174.1 | 20 | 9 | 20 | 12 |
Dopamine (DA) | 154.2 → 91.1 | 50 | 4 | 30 | 8 |
Oxytocin (OXT) | 1008.3 → 724.5 | 60 | 9 | 40 | 12 |
Nic-d3 | 166.1 → 132.1 | 70 | 10 | 20 | 10 |
Cot-d3 | 180.1 → 80.2 | 75 | 10 | 30 | 15 |
CRT-d4 | 367.1 → 121.4 | 70 | 10 | 30 | 10 |
5-HT-d4 | 181.2 → 164.3 | 25 | 5 | 15 | 3 |
MEL-d4 | 237.1 → 178.1 | 20 | 9 | 20 | 12 |
DA-d2 | 156.2 → 93.1 | 50 | 4 | 30 | 8 |
OXT-d5 | 1013.3 → 724.5 | 60 | 9 | 40 | 12 |
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Kataoka, H.; Miyata, S.; Ehara, K. Simultaneous Determination of Tobacco Smoke Exposure and Stress Biomarkers in Saliva Using In-Tube SPME and LC-MS/MS for the Analysis of the Association between Passive Smoking and Stress. Molecules 2024, 29, 4157. https://doi.org/10.3390/molecules29174157
Kataoka H, Miyata S, Ehara K. Simultaneous Determination of Tobacco Smoke Exposure and Stress Biomarkers in Saliva Using In-Tube SPME and LC-MS/MS for the Analysis of the Association between Passive Smoking and Stress. Molecules. 2024; 29(17):4157. https://doi.org/10.3390/molecules29174157
Chicago/Turabian StyleKataoka, Hiroyuki, Saori Miyata, and Kentaro Ehara. 2024. "Simultaneous Determination of Tobacco Smoke Exposure and Stress Biomarkers in Saliva Using In-Tube SPME and LC-MS/MS for the Analysis of the Association between Passive Smoking and Stress" Molecules 29, no. 17: 4157. https://doi.org/10.3390/molecules29174157