Ultrasound–Vortex-Assisted Dispersive Liquid–Liquid Microextraction Combined with High Performance Liquid Chromatography–Diode Array Detection for Determining UV Filters in Cosmetics and the Human Stratum Corneum
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Chemicals
2.2. The US–VA–DLLME Procedure
2.3. Instrumentation and Conditions
2.4. Method Validation
2.5. Cosmetics Application
2.6. Evaluating the Sunscreen-Removal Efficiency
2.7. Evaluating the UV Filter Concentration in Human Skin after Spreading a Sunscreen Sample on the Forearm
2.7.1. Single Applications of Sunscreen to the Skin with Different Exposure Times (0.5, 1, 4, and 8 h)
2.7.2. Double Application of the Sunscreen to the Skin (4 + 4 h)
3. Results and Discussion
3.1. Optimizing the US–VA–DLLME Procedure
3.1.1. Effect of the Dispersant
3.1.2. Effect of the Extractant
3.1.3. Effect of Vortexing and Ultrasonication
3.2. Method Validation
3.3. Cosmetics Analysis
3.4. Evaluating the Concentrations of UV Filter Residues in Human Skin after Exposure to Sunscreen
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Not available. |
Chromolith | ZORBAX 300SB | XBridge BEH | CORTECS | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Chemistry | C18 | C18 | C18 | C18 | ||||||||||||
I.D. (mm) | 2 | 2.1 | 2.1 | 2.1 | ||||||||||||
L (mm) | 100 | 100 | 50 | 50 | ||||||||||||
Particle Size (µm) | - | 3.5 | 2.5 | 2.7 | ||||||||||||
UV filters | k | α | N/m | Rs | k | α | N/m | Rs | k | α | N/m | Rs | k | α | N/m | Rs |
AV | 13.5 | 56,878 | 12.7 | 237,759 | 23.5 | 543,055 | 27.7 | 749,816 | ||||||||
1.0 | 0.2 | 1.0 | 0.9 | 1.0 | 1.5 | 1.0 | 1.6 | |||||||||
OMC | 13.7 | 73,457 | 13.0 | 352,883 | 24.5 | 389,656 | 28.9 | 478,847 | ||||||||
1.1 | 0.9 | 1.1 | 3.4 | 1.1 | 2.0 | 1.0 | 2.6 | |||||||||
OCT | 14.3 | 79,834 | 14.0 | 405,038 | 26.0 | 416,811 | 30.8 | 603,501 | ||||||||
- | - | - | - | - | - | - | - | |||||||||
EHT | 25.0 | 357,860 | 25.5 | 1,500,064 | 42.4 | 1,174,803 | 55.5 | 1,805,575 | ||||||||
- | - | - | - | - | - | - | - | |||||||||
BEMT | 28.7 | 316,880 | 26.8 | 881,338 | 47.3 | 928,022 | 62.8 | 837,478 |
UV Filters | Linear Range (µg/mL) | Determination Coefficient (r2) | LOD (ng/mL) | Interday (%, n = 6) a | Intraday (%, n = 6) a | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Q1 | Q2 | Q3 | Q1 | Q2 | Q3 | ||||||||||
RSD | RE | RSD | RE | RSD | RE | RSD | RE | RSD | RE | RSD | RE | ||||
AV | 0.05–5 | 0.999 | 15 | 1.9 | 3.3 | 2.8 | −4.0 | 1.2 | −1.9 | 1.6 | 0.2 | 0.4 | 1.8 | 0.8 | 2.2 |
OMC | 0.05–5 | 0.998 | 15 | 4.9 | 0.2 | 4.2 | −2.7 | 3.9 | 1.1 | 1.8 | 0.6 | 1.6 | 0.2 | 1.4 | 0.3 |
OCT | 0.1–10 | 0.999 | 15 | 2.8 | −0.8 | 3.1 | −2.6 | 1.2 | −1.5 | 1.4 | 0.5 | 0.8 | 2.5 | 0.3 | 0.8 |
EHT | 0.05–5 | 0.999 | 15 | 3.4 | −1.3 | 3.0 | −2.0 | 1.5 | −1.6 | 1.5 | −2.0 | 1.2 | −1.0 | 0.3 | −0.4 |
BEMT | 0.05–5 | 0.999 | 15 | 3.9 | −1.8 | 3.1 | −2.1 | 1.2 | −1.5 | 2.2 | −1.3 | 0.8 | −1.7 | 1.4 | −0.2 |
Instrumental Method | Pretreatment Method | Sample | Solvent | Linear Range (ng/mL) | LOD (ng/mL) | Analyte | Ref. |
---|---|---|---|---|---|---|---|
GC–MS | SPME | Fish tissue | 1000–7000 a | 5–25 a | OMC, OCT | [4] | |
HPLC–MS/MS | PLE | Cosmetics | MeOH | 1–1000 | 10–31 a | AV, OMC, OCT | [5] |
HPLC–MS/MS | UAE–dSPE | Human placenta tissue | ACN | 0.3–15 a | 0.1 a | OMC, OCT | [6] |
HPLC–MS/MS | QuEChERS–reverse SPE | Aquatic invertebrates | ACN | 0.1–25 | 2.0–3.3 a | OMC, OCT | [7] |
HPLC–DAD | SLE | Porcrine skin | DMF, EtOH | 10,000–50,000 | 280–1400 | BEMT, EHT | [8] |
HPLC–DAD | dilution | Cosmetics | MeOH, EA | 1800–250,000 | 32–67 | AV, OCT | [9] |
HPLC–DAD | US–VA–DLLME | Cosmetics, extracts of the human stratum corneum | MeOH, anisole | 50–5000; 100–10,000 b | 15 | AV, OMC, OCT, EHT, BEMT | This study |
UV Filters | o/w a | w/o a | ||||
---|---|---|---|---|---|---|
Found (μg/mL) | RSD (%) | Recovery (%) | Found (μg/mL) | RSD (%) | Recovery (%) | |
AV | 2.2 | 2.4 | 88.1 | 2.2 | 0.8 | 87.8 |
OMC | 2.5 | 2.3 | 100.2 | 2.5 | 2.6 | 100.2 |
OCT | 2.4 | 2.4 | 95.7 | 2.6 | 2.6 | 104.7 |
EHT | 2.5 | 3.3 | 99.4 | 2.5 | 3.7 | 99.4 |
BEMT | 2.5 | 5.4 | 100.6 | 2.5 | 2.3 | 98.4 |
UV Filters | Single | Twice | ||||||
---|---|---|---|---|---|---|---|---|
Cotton | S.C. | Cotton | S.C. | |||||
Mean [Range, μg] | RSD (%) | Mean [Range, μg] | RSD (%) | Mean [Range, μg] | RSD (%) | Mean [Range, μg] | RSD (%) | |
AV | 18.5 [8.6–37.4] | 46.0 | 14.7 [6.1–32.2] | 57.3 | 39.4 [22.2–49.9] | 20.5 | 23.6 [12.4–53.9] | 52.8 |
OMC | 18.0 [8.3–32.9] | 48.8 | 16.4 [7.4–27.9] | 41.0 | 42.2 [21.8–61.2] | 26.6 | 30.0 [16.1–47.8] | 46.2 |
OCT | 17.2 [8.9–29.6] | 38.0 | 14.1 [6.0–26.1] | 49.6 | 38.3 [22.8–50.6] | 21.2 | 23.6 [12.0–53.9] | 53.6 |
EHT | 5.8 [2.6–12.9] | 61.1 | 13.4 [5.3–27.6] | 51.3 | 18.2 [5.3–34.6] | 57.1 | 22.4 [10.6–43.5] | 44.7 |
BEMT | 5.6 [2.6–12.0] | 58.7 | 13.3 [5.7–28.1] | 52.4 | 18.2 [5.5–33.2] | 56.6 | 21.9 [11.1–41.5] | 42.8 |
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Liao, F.-Y.; Su, Y.-L.; Weng, J.-R.; Lin, Y.-C.; Feng, C.-H. Ultrasound–Vortex-Assisted Dispersive Liquid–Liquid Microextraction Combined with High Performance Liquid Chromatography–Diode Array Detection for Determining UV Filters in Cosmetics and the Human Stratum Corneum. Molecules 2020, 25, 4642. https://doi.org/10.3390/molecules25204642
Liao F-Y, Su Y-L, Weng J-R, Lin Y-C, Feng C-H. Ultrasound–Vortex-Assisted Dispersive Liquid–Liquid Microextraction Combined with High Performance Liquid Chromatography–Diode Array Detection for Determining UV Filters in Cosmetics and the Human Stratum Corneum. Molecules. 2020; 25(20):4642. https://doi.org/10.3390/molecules25204642
Chicago/Turabian StyleLiao, Fang-Yi, Yu-Lin Su, Jing-Ru Weng, Ying-Chi Lin, and Chia-Hsien Feng. 2020. "Ultrasound–Vortex-Assisted Dispersive Liquid–Liquid Microextraction Combined with High Performance Liquid Chromatography–Diode Array Detection for Determining UV Filters in Cosmetics and the Human Stratum Corneum" Molecules 25, no. 20: 4642. https://doi.org/10.3390/molecules25204642