Читать книгу Fundamentals of Analytical Toxicology - Robin Whelpton - Страница 4

1 Chapter 1Figure 1.1 The three key steps in systematic toxicological analysisFigure 1.2 Reaction of amfetamine with acetone

2 Chapter 2Figure 2.1 Volumetric blood microsampling devices. (a) Mitra (Neoteryx) uses...Figure 2.2 Schematic of head hair collection

3 Chapter 3Figure 3.1 Histogram of replicate absorbance measurements (n = 44) for plasm...Figure 3.2 Excel table of results for one-way ANOVA of the data of Table 3.3...Figure 3.3 The principle of least-squares regressionFigure 3.4 The effect of the number of data points on the 95 % confidence in...Figure 3.5 Testing calibration curves for linearity: (a) data fitted to a st...Figure 3.6 The data of Figure 3.5(a) fitted (a) to a quadratic function and ...Figure 3.7 Calibration data for GC-ECD of medazepam fitted to (a) a hyperbol...Figure 3.8 Use of residual plots to ascertain the most appropriate method to...Figure 3.9 Calibration curve for the method of standard additionsFigure 3.10 Extraction characteristics of morphine (•), N-ethylnormorphine (...Figure 3.11 Synthesis of ISTDs from readily available starting materials to ...Figure 3.12 Linear regression to compare results from two laboratories showi...Figure 3.13 Comparison of linear regression (a) and Bland–Altman plot (b) us...Figure 3.14 Quality of life scores from patients receiving placebo, or drug ...Figure 3.15 Example of Theil's incomplete method for non-parametric calibrat...Figure 3.16 Examples of quality control charts: (a) Shewhart (b) J-ChartFigure 3.17 An example of an EQA scheme report (plasma olanzapine)

4 Chapter 4Figure 4.1 Summary of the steps that may be involved in an analysisFigure 4.2 Microextraction procedure flow-diagrams: (a) prior to GC; (b) pri...Figure 4.3 Extraction of imipramine and three metabolites from buffers of va...Figure 4.4 Schematic diagram of a solid phase extraction procedureFigure 4.5 HybridSPE-Phospholipid technologyFigure 4.6 Solid phase microextraction: (a) spring-loaded solid probe coated...Figure 4.7 Equilibration time profile for SPME of lidocaine from plasma afte...Figure 4.8 Schematic of modes of liquid phase microextraction: (a) single dr...Figure 4.9 Supercritical fluid extraction. (a) Phase diagram for a fluid. (b...Figure 4.10 Schematic diagram of apparatus for accelerated solvent extractio...Figure 4.11 Diagrammatic representation of equilibrium dialysis. (a) Equilib...

5 Chapter 5Figure 5.1 The basic components of a single-beam spectrophotometerFigure 5.2 Diagram of a typical optical-null double-beam spectrophotometerFigure 5.3 Diagram of a linear diode array detectorFigure 5.4 Measurement of carboxyhaemoglobin (note the wavelength expansion ...Figure 5.5 Conway microdiffusion. (a) Apparatus. (b) Qualitative detection o...Figure 5.6 Diagram of a double-grating spectrophotofluorimeter (based on the...Figure 5.7 Excitation and emission spectra of quinine (1 mg L^–1) in de...Figure 5.8 Some compounds that exhibit natural fluorescenceFigure 5.9 Chemiluminescent reaction of luminol with hydrogen peroxideFigure 5.10 Hydrogen peroxide oxidation of TCPOFigure 5.11 A simple luminometerFigure 5.12 Schematic diagram of laser Raman spectroscopy

6 Chapter 6Figure 6.1 Preparation of immunogen for chlorpromazine radioimmunoassayFigure 6.2 Directing antibody formation for a class-selective and an analyte...Figure 6.3 Principle of competitive bindingFigure 6.4 Reaction of tetramethylbenzidine with hydrogen peroxide in the pr...Figure 6.5 Comparison of (a) antigen-labelled and (b) antibody-labelled ELIS...Figure 6.6 Representation of sandwich ELISA microplate well after its second...Figure 6.7 Principle of enzyme-multiplied immunoassay technique (a) without ...Figure 6.8 Principle of fluorescence polarization immunoassay: (a) without a...Figure 6.9 Principle of cloned enzyme donor immunoassay. (a) No added drug a...Figure 6.10 Different modes of measurement for turbidimetric assaysFigure 6.11 RIA calibration graphs showing original data (a) transformed to ...Figure 6.12 Alcohol dehydrogenase catalyzed oxidation of ethanolFigure 6.13 Oxidation of ethanol catalyzed by alcohol oxidaseFigure 6.14 Reaction of Ellman's reagent with thiols

7 Chapter 7Figure 7.1 Elution chromatography: retention timeFigure 7.2 Schematic representation of a fractionating column showing the co...Figure 7.3 Chromatographic efficiency: (a) measurement of H; (b) effect of m...Figure 7.4 Effect of particle size and linear velocity on H using ∼2 μm size...Figure 7.5 Kinetic plots (t_M/N² against plate number) for two packing materi...Figure 7.6 Effect of efficiency on resolution of A and B. Values calculated ...Figure 7.7 Measurement of peak asymmetry

8 Chapter 8Figure 8.1 Thin-layer chromatography: schematic and calculation of R_f values...Figure 8.2 Comparison of the migration of the solvent front in saturated and...Figure 8.3 Example of differential visualization of a TLC plate (Flanagan et...Figure 8.4 Hydrolysis of benzodiazepines and dealkylation of N-alkylbenzophe...Figure 8.5 Two modes of forced-flow planar chromatography (Bryston & Papilla...

9 Chapter 9Figure 9.1 Block diagram of a gas chromatographFigure 9.2 Split/splitless injector for gas chromatographyFigure 9.3 Schematic of (a) GC thermal desorption unit; (b) modes of useFigure 9.4 Schematic diagram of a GC thermal conductivity detectorFigure 9.5 Schematic diagram of a GC flame ionization detectorFigure 9.6 Schematic diagrams of (a) nitrogen–phosphorus detector and (b) el...Figure 9.7 Schematic diagram of a pulsed discharge helium ionization detecto...Figure 9.8 Schematic diagram of a GC vacuum UV detectorFigure 9.9 Structures of polysiloxane and polyethylene glycol stationary pha...Figure 9.10 Schematic of a fused silica capillary GC columnFigure 9.11 Schematic diagram of 2D-GCFigure 9.12 GC headspace vialFigure 9.13 Examples of chemically bonded chiral phases. (a) β-CD bonde...Figure 9.14 Extracted negative ion chromatograms (GC-MS) of R-/S-enantiomers...

10 Chapter 10Figure 10.1 Schematic diagram of a dual pump gradient LC system with high-pr...Figure 10.2 Structure of polyoxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-...Figure 10.3 LC pump head during a filling strokeFigure 10.4 Six-port LC injection valve showing (a) load and (b) inject posi...Figure 10.5 Schematic diagram of UV/visible detector flow cell for LCFigure 10.6 Schematic diagram of a combined fluorescence/UV detector cell fo...Figure 10.7 Simplified designs of LC-ED cells. (a) Thin-layer cell, (b) Wall...Figure 10.8 Schematic diagram of chemiluminescent nitrogen detector (Nussbau...Figure 10.9 Schematic diagram of a charged aerosol detector (Magnusson et alFigure 10.10 Arrangement for post-column reagent addition in liquid chromato...Figure 10.11 Example of a bridged ethylsiloxane/silica hybrid LC packingFigure 10.12 Schematic diagram of affinity chromatographyFigure 10.13 Typical calibration curve for size exclusion chromatographyFigure 10.14 Representation of chiral recognition. The structure with three-...Figure 10.15 Analysis of 3,5-dinitrobenzamide derivatives of (a) amfetamine,...Figure 10.16 Derivatization of racemic amfetamine to provide points of inter...Figure 10.17 Effect of the nature of the column packing on the liquid chroma...Figure 10.18 Liquid chromatography of lidocaine using Waters Spherisorb S5 S...

11 Chapter 11Figure 11.1 (a) Phase diagram for carbon dioxide. (b) Effect of addition of ...Figure 11.2 Schematic diagram of a packed column supercritical fluid chromat...Figure 11.3 Schematic diagram of supercritical fluid chromatography pressure...Figure 11.4 Resolution of warfarin enantiomers on a CHIRALPAK AD column in (...Figure 11.5 Chemical formulae of ketamine and selected metabolitesFigure 11.6 Supercritical fluid chromatography of JWH-073. (a) Blank urine; ...

12 Chapter 12Figure 12.1 Schematic diagram of the arrangement for capillary electrophores...Figure 12.2 Diagram showing how electro-osmotic flow carries analytes to the...Figure 12.3 Principle of micellar electrokinetic capillary chromatographyFigure 12.4 Elution time window for non-ionized species in MEKCFigure 12.5 Micellar electrokinetic capillary chromatography of some misused...Figure 12.6 Sample electropherograms of (a) blank EBC, (b) an EBC sample spi...

13 Chapter 13Figure 13.1 Schematic diagram of a double sector mass spectrometerFigure 13.2 Schematic diagram of a quadrupole mass spectrometerFigure 13.3 Schematic diagram of an ion trap quadrupole mass spectrometerFigure 13.4 Schematic diagram of a triple-quadrupole mass spectrometer (Tand...Figure 13.5 Schematic diagram of Q3 in a QTrap system. (a) Quadrupole and ex...Figure 13.6 Schematic diagram of a common time-of-flight tandem MS (QTOF) (r...Figure 13.7 Schematic diagram of an orbitrap tandem mass spectrometer (Q-Exa...Figure 13.8 Schematic side-view of an electron ionization sourceFigure 13.9 Schematic diagram of a typical GC-C-IRMS Instrument: configured ...Figure 13.10 Ion suppression. Response after injection of (i) an extract of ...Figure 13.12 Electrospray ionization: schematic of the mechanism of ion form...Figure 13.11 Schematic of an electrospray ionization interfaceFigure 13.13 Schematic of the components of an atmospheric pressure chemical...Figure 13.14 Atmospheric pressure chemical ionization: explanation of corona...Figure 13.15 Schematic diagram of an APPI interfaceFigure 13.16 Analytical figures of merit versus analytical throughput of chr...Figure 13.17 (a) Scheme of FIA-MS with LC autosamplers. (b). Diagram of a FI...Figure 13.18 Schematic diagrams of (a) DART ionization and (b) ESI or EASI s...Figure 13.19 Analysis of a dried blood spot by paper spray-MS (Reprinted fro...Figure 13.20 Schematic diagram of a laser diode thermal desorption sourceFigure 13.21 Principle of matrix assisted laser desorption/ionization mass s...Figure 13.22 Typical MALDI applications in forensic toxicology: (a) high-thr...Figure 13.23 Typical GC-MS total ion chromatogram of a methanolic solution c...Figure 13.24 Mass spectra of citalopram (M_r 324.4) and clomipramine (M_r 314....Figure 13.25 EI mass spectra of amfetamine (M_r 135.2) and metamfetamine (M_r ...Figure 13.26 EI mass spectra of the 4-carboxyhexafluorobutyryl (4-CHFB) deri...Figure 13.27 Problems associated with deuterated internal standards. (a) Sep...Figure 13.28 Isotopic internal calibration in LC-MS/MS: plasma clozapine and...Figure 13.29 MALDI-MS/MS images of (a) longitudinal sectioned drug user hair...

14 Chapter 14Figure 14.1 Schematic diagram of a basic ion mobility spectrometerFigure 14.2 (a) Reactant ion peak and dimerization (O'Donnell et al., 2008–r...Figure 14.3 Basic ion mobility spectrometry operation. (a) Temporal. (b) Spa...Figure 14.4 High field asymmetric waveform ion mobility spectrometry. (a) Wa...Figure 14.5 A stacked ring guide in travelling wave ion mobility spectrometr...Figure 14.6 Trapped ion mobility spectrometryFigure 14.7 Ion mobility spectrometry-mass spectrometry. (a) Drift time ion ...Figure 14.8 Schematic diagram of SIFT-MS (Smith & Španěl, 2011–reproduced wi...Figure 14.9 Ion mobility spectrometry of codeine in synthetic urine (Midey e...Figure 14.10 FAIMS compensation voltage scans for a mixture of hydromorphone...Figure 14.11 Ion mobility spectrometry of atenolol. (a) Analysis of individu...

15 Chapter 15Figure 15.1 Distribution of aspirin (pK_a = 3.4) between gastric fluid and pl...Figure 15.2 Some of the factors that may reduce oral availability. Other fac...Figure 15.3 The effect of pH on the distribution of salicylate (pK_a = 3.0) b...Figure 15.4 Some metabolic pathways of diamorphine, morphine, and codeineFigure 15.5 Role of xanthine oxidase in the metabolism of purinesFigure 15.6 Reduction of nitrazepam by human aldehyde oxidase (AOX1)Figure 15.7 Conjugation of salicylic acid to produce the β-D-glucuronid...Figure 15.8 Examples of drugs metabolized by N-acetylation. The acetylated n...Figure 15.9 Metabolic pathways of phenacetin and paracetamolFigure 15.10 Conjugation of salicylic acid with glycineFigure 15.11 Stereochemical biotransformations. (a) Hydroxylation and reduct...Figure 15.12 Some metabolic pathways of olanzapineFigure 15.13 Metabolism of selected 7-chlorobenzodiazepines and their prodru...Figure 15.14 Selected metabolic pathways of midazolam in humansFigure 15.15 Reduced and oxidized metabolites of sulindacFigure 15.16 Oxidative debromination of halothaneFigure 15.17 Metabolism of dichloromethane: (a) microsomal and (b) cytosolic...Figure 15.18 Comparative metabolic pathways of malathion in mammals and in i...Figure 15.19 Trans-esterification of methylphenidate in the presence of etha...Figure 15.20 Mean plasma concentrations of nortriptyline after a single oral...

16 Chapter 16Figure 16.1 First-order elimination curves: (a) C vs t, (b) ln C vs t, and (...Figure 16.2 Concentration–time curves showing first-order input into a singl...Figure 16.3 (a) Constant rate infusion into a single-compartment model showi...Figure 16.4 Plasma concentration–time plots following repeated doses at equa...Figure 16.5 Principle of sustained-release preparations. k_a < λ so it is rat...Figure 16.6 (a) Steady-state serum concentrations of phenytoin in five subje...Figure 16.7 Plasma 2,4-D concentrations (♦), urinary excretion (*), and urin...Figure 16.8 Decay from a two-compartment kinetic model following a i.v. bolu...Figure 16.9 The trapezoidal method of measuring AUC (Inset: measurement of t...Figure 16.10 Effect of (a) food and (b) pH on the oral absorption of ketocon...Figure 16.11 Effects of age on (a) relative distribution of lean body weight...Figure 16.12 Example of a typical BAC versus time curve (Jones, 2010–reprodu...Figure 16.13 Simulated curves showing the effect of the rate of absorption o...

17 Chapter 17Figure 17.1 Principle of lateral flow immunoassayFigure 17.2 Comparison of the sensitivities of three oral fluid testing devi...Figure 17.3 (a) Example of a Drugwipe Twin II. (b). Exploded view showing wi...

18 Chapter 18Figure 18.1 Typical detection window for drugs of misuse in various common b...Figure 18.2 An example of an oral fluid collection device (Salivette™, Sarst...Figure 18.3 Differentiation between (a) contaminated hair and (b) cocaine us...Figure 18.4 The SensAbues exhaled air condensate collection system (Beck et...

19 Chapter 19Figure 19.1 GC-FID of a whole blood sample obtained post-mortem from a patie...Figure 19.2 HS-GC of ethanol and other volatile compounds: (a) FID and (b) M...Figure 19.3 (a) Merged GC-NCI mass chromatograms of characteristic ions of h...Figure 19.4 Merged mass fragmentograms of extracted serum standards containi...Figure 19.5 Reconstructed mass chromatograms of an acetylated extract of a 2...Figure 19.6 Mass spectrum of the peak at 8 min (Figure 19.5), the reference ...Figure 19.7 Mass fragmentograms of the quantifiers (m/z) of a plasma sample ...Figure 19.8 LC-DAD of a dichloromethane extract (pH 9) of a blood sample fro...Figure 19.9 Typical LC-MS total ion chromatogram obtained on analysis of a m...Figure 19.10 Extracted ion chromatograms of the precursors of test compounds...Figure 19.11 Identification of dabigatran metabolites in a sample from a 66-...

20 Chapter 20Figure 20.1 Schematic representation of parameters that have been used for T...Figure 20.2 Metabolic pathways of methylxanthinesFigure 20.3 Metabolism of chloroquine and hydroxychloroquine

21 Chapter 21Figure 21.1 Energy level diagrams to show transitions associated with (a) AE...Figure 21.2 Pneumatic nebulizer for flame AASFigure 21.3 Inductively coupled plasma: (a) ICP torch (b) components of an I...Figure 21.4 Example of ICP-MS mass spectrum (courtesy of Thermo-Fisher Scien...Figure 21.5 Hydride generation AASFigure 21.6 Cold vapour generationFigure 21.7 Schematic diagram of anodic stripping voltammetry. Metal ions pl...Figure 21.8 An example of an effective calcium exchanger

22 Chapter 22Figure 22.1 Mammalian metabolism of selected alcoholsFigure 22.2 Some synthetic anabolic steroidsFigure 22.3 Median blood clozapine and norclozapine concentrations before an...Figure 22.4 Comparison of the chemical structures of selected designer benzo...Figure 22.5 Some examples of laxativesFigure 22.6 Selected examples of hallucinogens: (a) N-benzylphenylethylamine...Figure 22.7 Interaction of cystine with cyanideFigure 22.8 Selected metabolic pathways of (R)-ketamineFigure 22.9 Metabolism of tramadolFigure 22.10 Some metabolites and decomposition products of cocaine