Introduction
No., year | Analyte(s) | IS(s) | Matrix(es) | Analytical method(s) | Pretreatment | Validation results and remark(s) | Reference |
---|---|---|---|---|---|---|---|
1. 2012 | GHB | GHB-d6 | Scalp hair | GC–MS, LC–MS/MS | Hair digest by NaOH with IS only or with IS + each calibration standard; LLE with EtOAc; extract derivatization with BSTFA + TMCS for GC‒MS; the above extract before derivatization also used for LC–MS/MS | Endogenous GHB in hair measured by SAM with 4 point calibration; 0.28 ng/mg by GC–MS, and 0.27 ng/mg by LC–MS/MS. The validation data for SAM were not given clearly | [48] |
2. 2013 | 25I-NBOMe | 25H-NBOMe | Brain, liver, gastric contents, bile, blood, urine | LC–MS/MS | Homogenization of the sample with IS only or with IS + each calibration standard; purification by SPE | SAM with 4 point calibration was used for quantification of the target compound for 2 solid tissues, gastric contents and bile. No validation data were given for SAM | [49] |
3. 2013 | EG, PG, DEG | EG-d6, PG-d8, DEG-d8 | AM whole blood | GC–MS | The sample mixed with ISs only or with ISs + respective calibration standard mixture; extraction + deproteinization with MeCN; derivatization with HFB anhydride; LLE with n-hexane | SAM calibration equations, intraday and interday repeatabilities (%RSD), LOQs, and recovery rates were all satisfactory | [23] |
4. 2014 | α-Pyrrolidinobutiophenone | α-PVP | PM whole blood, CSF, urine, stomach contents, five solid tissues | LC–MS/MS | A fluid specimen mixed with IS only or with IS + each calibration standard, and added with MeCN; the solid tissue homogenized by a Polytron homogenizer and spiked with IS only or with IS + each calibration standard; added with MeCN for mixing and centrifugation; MeCN extracts for both body fluid and solid tissue again extracted by the QuEChERS method | LOD, SAM linearity, intraday and interday repeatabilities (%RSD), matrix effects, and recovery rates were all satisfactory | [25] |
5. 2014 | EG, PG, DEG | EG-d6, PG-d8, DEG-d8 | Urine of healthy subjects | GC–MS | The same pretreatments as those of no. 3 | LOQs, SAM linearities, intraday and interday repeatabilities (%RSD), and recovery rates were all satisfactory | [26] |
6. 2014 | EG, PG | EG-d6, PG-d8 | PM whole blood, urine, and seven solid tissues | GC–MS | The same pretreatments as those of no. 3 | SAM regression equations, intraday and interday repeatabilities (%RSD) and recovery rates were all satisfactory | [27] |
7. 2014 | α-PVP, hydroxyl-α-PVP (metabolite) | α-PBP | PM whole blood, urine, stomach contents, and seven solid tissues | LC–MS/MS | Solid tissues homogenized by bead beater-type homogenizer; tissue homogenates or fluidal specimens spiked with IS only or with IS + respective calibration standard mixture; each supernatant subjected to SPE | LODs, SAM linearities, intraday and interday repeatabilities (%RSD), and recovery rates were all satisfactory, but matrix effects (%bias) were at − 89.5 to + 3.36% | [28] |
8. 2014 | PV9 | PV8 | AM whole blood and urine, PM whole blood | LC–MS/MS | Body fluids spiked with IS only or with IS + each calibration standard; QuEChERS extraction performed | SAM equations, intraday and interday repeatabilities (%RSD), matrix effects and recovery rates were all satisfactory | [29] |
9. 2014 | Diphenidine, 5-fluoro-AB-PINACA | Phencyclidine | Herbal product | MALDI-QTOF-MS, GC–MS, direct flow injection ESI–MS/MS | Sonication of plant debris with methanol; dilution of the supernatant 1000- or 10,000-fold; to each diluted sample, IS only or IS + respective calibration standard mixture spiked | Tentative identification was made by MALDI-TOF–MS; the final identification was made by product ion spectrum comparison; the quantification of both compounds was made through SAM by GC–MS; the correlation coefficients of the SAM equations were greater than 0.99. Other validation parameters were not investigated | [30] |
10. 2014 | Atractyloside, corboxyatractyloside (natural toxins) | Oxazepam-d5 | Roots of a plant Atractylis gummifera L, whole blood of the consumer woman | HPLC–HR-MS | Crashing the dried roots; LLE with MeCN/water, (50:50, v/v); supernatant spiked with IS only or with IS + respective calibration standard mixture | By the SAM, only the concentrations of the toxins in roots were measured. The validation data for SAM determinations are not given. The analysis and validation for whole blood from a woman were done by the conventional MMCM | [50] |
11. 2015 | AB-CHMINACA, 5-fluoro-AMB, diphenidine | 5-Fluoro-AB-PINACA, phencyclidine | PM whole blood, urine, eight solid tissues | LC–MS/MS | Body fluids vortexed and centrifuged to obtain the supernatants; the solid tissues homogenized by a bead beater-type shaking machine; each aliquot of the sample solution spiked with ISs only or ISs + respective calibration standard mixture; subjected to QuEChERS extraction and filtration through a Captiva ND Lipids cartridge | All SAM equation, LODs, LOQ, intraday and interday repeatabilities, matrix effects and recovery rates were all satisfactory | [31] |
12. 2015 | Metformin | Not used | PM whole blood | LC–MS/MS | The specimen diluted tenfold with water; each aliquot not added or added with each calibration standard, precipitated with methanol, and centrifuged; the supernatant again diluted with water before analysis | SAM study was done as model experiments only with bovine blank whole blood or blank autopsy blood fortified with metformin. They presented all validation data following the conventional MMCM, despite the study for SAM | [45] |
13. 2015 | 5-Fluoro-ADB | 5-Fluoro-AMB | PM whole blood, urine, stomach contents, nine solid tissues, some herbal products | LC–MS/MS | The treatment procedures for cadaver matrices essentially the same as described in no. 11 using bead beater-type homogenization machine; the QuEChERS extraction and filtration with Captiva ND Lipids cartridges before analyses | The SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects and recovery rates were all within the acceptable ranges | [32] |
14. 2015 | PV9 | PV8 | Nine solid tissues collected from a cadaver | LC–MS/MS | The treatment procedure almost the same as that described in no. 11 | The SAM calibration equations, LODs, intraday and interday repeatabilities, matrix effects and recovery rates all within the acceptable ranges | [33] |
15. 2015 | MAB-CHIMINACA, 5-fluoro-ADB-PINACA | AB-CHMINACA, 5-fluoro-AB-PINACA | PM whole blood, pericardial fluid, stomach contents, nine solid tissues | LC–MS/MS | The treatment procedure almost the same as that described in no. 11 | The SAM equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects and recovery rates all within the acceptable ranges | [34] |
16. 2016 | Flunitrazepam, 7-aminoflunitrazepam | Nimetazepam | PM whole blood, bile, eight solid tissues | LC–MS/MS | The treatment procedure almost the same as that described in no. 11 | The SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects and recovery rates for both compounds were all within the acceptable ranges | [35] |
17. 2016 | Diphenidine | α-Cyano-4-hydroxyl-cinnamic acid | Frozen tissue sections of five solid tissues, which contained preexisting diphenidine | Direct-MALDI-QTOF-MS | Place each diphenidine calibration standard (in 75% methanolic solution) on each target well (0, 0.1, 1.0, or 10 ng/well); evaporate the calibration solvent on each well; put 10 µm-thick tissue section containing preexisting diphenidine cut at -20℃ over each dried calibrator on the target well; the plate carrying the sections desiccated for about 18 h at 25℃; the matrix solution (α-cyano-4-hydroxycinnamic acid) sprayed over the entire surface of the desiccated plate with dried sections | This is a unique application of the SAM; it is difficult to perform accurate quantification of diphenidine in tissue sections; the presence of as many as 198 target wells enabled the simultaneous semiquantification of diphenidine in many tissue sections; this is advantageous of this method, which requires many determinations for SAM calibration. This method enabled histological localization of diphenidine with millimeter graduation | [36] |
18. 2016 | Methamphetamine, amphetamine | Methamphetamine-d5, amphetamine-d7 | Postmortem whole blood from nine locations, pericardial fluid, bile, stomach contents, eight solid tissues | LC–MS/MS | The treatment procedure was the almost the same as that described in no. 11 | This study was focused on redistribution of amphetamines in nine locations of blood vessels. There were great differences in amphetamines according to the blood locations. The SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects and recovery rates were all satisfactory | [37] |
19. 2016 | GHB | GHB-d6 | Scalp hair | GC–MS | The pretreatment procedure was almost the same as that described in no. 1 | The authors tried to quantify endogenous GHB in hair samples collected from as many as 150 subjects. Although they described the use of the SAM, no clear details of its validation were given | [51] |
20. 2017 | JWH-210, RCS-4, THC, their metabolites | THC-d8, HO-THC-d3, THC-COOH-d3, JWH-210-d9, RCS-4-d9 | Pig 12 solid tissues, bile | LC–MS/MS | Live pigs received administration of the mixture of the parent drugs i.v.; after 6 h, the animals killed, and solid tissues and body fluids collected; the samples homogenized with water in the presence or absence of respective calibration standard mixture; the mixture of ISs also added to all homogenate samples; incubations with β-glucuronidase /arylsulfatase, followed by SPE purification | The calibrators used for each matrix containing preexisting analytes were only three points, i.e., only four including a point without the calibration standard | [52] |
21. 2018 | 4-MEC, MDPV, methoxetamine, α-PVP | MBDB-d5 | PM whole blood, bile, stomach contents, five solid tissues | LC–MS/MS | Each tissue homogenate or body fluid spiked with IS only or IS + respective calibration standard mixture, followed by automated SPE extraction; in another group, each solid tissue or body fluid spiked with IS only or IS + respective calibration standard mixture, followed by the QuEChERS extraction and filtration through a Captiva ND Lipids cartridge; all validations followed the MMCM | All analytic concentrations were obtained by the SAM with only three calibrators, i.e., 4-point calibration; the validation experiments were carried out by those of the conventional MMCM using the blank matrices collected from other cadavers without exposure to the target drugs | [44] |
22. 2018 | EAM-2201, AB-PINACA, AB-FUBINACA, α-PVP | AB- CHMINACA | PM whole blood, three solid tissues | LC–MS/MS | Blood or tissue homogenate spiked with IS only or IS + respective calibration standard mixture; subjected to LLE with 1-chlorobutane in the presence of K2CO3; each solid tissue homogenized using the bead beater-type shaking machine | The correlation coefficients obtained from the SAM calibration equations were not less than 0.90. LODs, accuracies, precisions (not repeatabillities), recoveries and matrix effects were within the acceptable ranges | [38] |
23 2018 | Zolpidem, zolpidem phenyl-4-carboxylic acid | Zolpidem-d7, zolpidem phenyl-4-carboxylic acid-d4 | PM whole blood, pericardial fluid, bile, stomach contents, urine, eight solid tissues | LC–MS/MS | The treatment procedure almost the same as that described in no. 11 | The correlation coefficients of SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects, recovery rates and stability were all within the acceptable ranges | [39] |
24. 2019 | Mepirapim, acetyl fentanyl | JWH-200, acetyl fentanyl-d5 | PM whole blood, urine, nine solid tissues | LC–MS | Each body fluid or solid tissue thoroughly homogenized with blender; each sample suspension spiked with ISs only or ISs + respective calibration standard mixture in the presence of Na2CO3; loaded onto an Isolute SLE + column; then eluted with tert-butyl ether | The SAM calibration equations, LODs, inraday and interday repeatabilities, matrix effects and recovery rates were all within acceptable ranges | [56] |
25. 2019 | 5F-ADB | Not used | PM whole blood | HPLC–UV | Blood sample subjected to extractive deproteinization with MeCN;. LLE with ethyl acetate under alkaline conditions | Only linearity range, LOD and recovery rate were described without the details of SAM validation procedure | [47] |
26. 2019 | Clitidine | Kainic acid | Paralepistopsis acromelalga mushrooms | LC–MS/MS | Homogenized by the bead beater-type shaking machine in the presence of 50% methanol; diluted 100-fold with 50% methanol and centrifuged; to the diluted sample, IS only or IS + each calibration standard spiked and passed through a Captiva ND Lipids cartridge | The SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, and recovery rates were all within acceptable ranges; the depressive matrix effects were found for clitidine in the caps of the mushrooms (49.5%) | [40] |
27. 2019 | JWH-210, RCS-4, THC, their metabolites | THC-d3, HO-THC-d3, THC-COOH-d3, JWH-210-d9, RCS-4-d9 | Pig jugular vein blood, cardiac blood, bile, duodenum contents, six solid tissues | LC–MS/MS | Pigs received a single pulmonary dose of drug mixture by inhalation of their vapor.; after 8 h, the animals killed with w61; the solid tissues and body fluids homogenized, and each suspension spiked with the ISs only or ISs + respective calibration standards; incubation with β-glucuronidasese/arylsulfatase followed by purification with SPE | This study is the continuation of the previous no. 20 with intravenous administration by the same research group. This study deals with different administration route, i.e., the inhalation of drug vapor via the airway. Also in this paper, no mentions on the validation of the SAM used were made | [53] |
28. 2020 | 4-Chloroethcathinone, N-ethylnorpentylone, N-ethylhexedrone, 4-fluoro-α-pyrrolidinohexiophenone | Trimipramine-d3 | Blood plasma of users | LC–MS/MS | Deproteinization plus extraction with MeCN; each supernatant mixed with IS only or IS + respective calibration standard mixture, followed by centrifugation | Each SAM calibration curves was constructed with six concentration points. No validation data for the SAM were presented | [54] |
29. 2020 | Isotonitazene | Fentanyl-d5 | PM blood, urine, vitreous fluid from 18 authentic forensic cases | LC–MS/MS | Each fluid sample spiked with IS only or IS + each calibration standard; LLE with 1-chrolobutane/ethyl acetate (70:30, v/v), followed by shaking and centrifugation | Each SAM calibration curve with three points of standard addition (four points including one without the standard addition) showed that the coefficient of determination was 0.999; LODs < 0.02 ng/mL; recovery rate 89%. However, no details of the SAM validation used were given | [55] |
30. 2020 | Buformin | Phenformin | PM whole blood, CSF, pericardial fluid, bile, small intestine contents, stomach contents, urine, eight solid tissues | LC–MS/MS | The treatment procedure was the almost the same as that described in no. 11 | The SAM calibration equations, LODs, LOQs, intraday and interday repeatabilities, matrix effects, recovery rates and stabilities at 25℃ were all within the acceptable ranges. The blood concentrations of buformin in this case were two or three orders of magnitude higher than those with its therapeutic doses | [41] |
31. 2020 | AB-FUBINACA metabolites (M3: butanoic acid metabolite, M4: amido hydrolytic metabolite) | 5F-NNEI | Lung, liver, kidney, urine of an abuser | LC–MS/MS | For solid tissues, homogenization with a bead beater-type shaking machine with acetonitrile; each homogenate supernatant spiked with IS only or IS + respective calibration standard mixture; for urine samples, the hydrolysis with β-glucuronidase conducted | Each SAM calibration curve with six points including zero calibrator was constructed, where the correlation coefficients were not lower than 0.992. LODs, accuracies, recovery rates and matrix effects were within acceptable ranges; but the urine analysis validation was conducted by the conventional MMCM because of less laboriousness | [42] |