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Examination of Firearms Review: 2007 to 2010 - Interpol

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Reverse phase liquid chroma<strong>to</strong>graphy (RPLC) has been widely used in<br />

bioanalysis, but very polar compounds may be weakly retained. With the use<br />

<strong>of</strong> a hydrophilic stationary phase and low-aqueous/ high-organic mobile phase,<br />

hydrophilic interaction chroma<strong>to</strong>graphy (HILIC) has been demonstrated <strong>to</strong> be a<br />

powerful technique for the retention <strong>of</strong> polar analytes [247]. HILIC also proved<br />

<strong>to</strong> improve MS sensitivity, allow higher flow rates, and reduce matrix effects<br />

[248]. Because <strong>of</strong> its advantages over RPLC, there is an increased interest in<br />

using HILIC in bio-analytical applications for drugs and their metabolites, which<br />

are <strong>of</strong>ten polar in nature [244,249]. For example, cocaine and its metabolites,<br />

especially ecgonine methyl ester, in hair samples [250], omeprazole and<br />

lansoprazole in plasma [251], me<strong>to</strong>clopramide in plasma [252], estrogen<br />

conjugates in urine [253], and acetylcholine, choline, and butyrobetaine in liver<br />

tissues [254]. Analysis <strong>of</strong> polar analytes, such as the endogenous metabolite<br />

trigonelline and the polar antibiotics amoxicillin in urine, using HILIC coupled <strong>to</strong><br />

NMR and MS, was also reported [255]. Analysis <strong>of</strong> EtG, could also be<br />

performed by HILIC-MS/MS instead <strong>of</strong> GC; the latter requires derivatisation<br />

[256].<br />

Although HILIC gives good separations <strong>of</strong> polar compounds, neutral and<br />

non-polar analytes generally show little retention [257]. To broaden the elution<br />

window, pharmaceutical compounds were analysed using serial coupling <strong>of</strong><br />

reversed-phase and hydrophilic interaction liquid chroma<strong>to</strong>graphy<br />

(RPLC/HILIC) [258]. In addition, the use <strong>of</strong> low-aqueous/ high-organic mobile<br />

phases in HILIC makes it possible for the eluent from SPE or liquid-liquid<br />

extraction (LLE) <strong>to</strong> be directly injected <strong>to</strong> the HILIC column without<br />

reconstitution, enabling high throughput and au<strong>to</strong>mated extractions<br />

[247,251,255].<br />

3.1.3 Capillary electrophoresis<br />

The current application <strong>of</strong> capillary electrophoresis (CE) in forensic <strong>to</strong>xicology<br />

has been reviewed with special focus on those areas where this technique has<br />

shown real advantages over chroma<strong>to</strong>graphic methods, such as chiral drugs,<br />

proteins, and alcohol biomarkers analyses [259].<br />

The utilization <strong>of</strong> dynamic doubly coated capillaries for a fast separation <strong>of</strong><br />

methadone and its two major metabolites,<br />

2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and<br />

2-ethyl-5-methyl-3,3-diphenyl-1-pyrroline (EMDP), was investigated. Complete<br />

648

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