Chemiluminescence detection of opium poppy (Papaver somniferum) alkaloids.

A review with 98 references. The determination of the opium poppy (Papaver somniferum) alkaloids and their semi-synthetic derivatives has important applications in industrial process monitoring, clinical analysis and forensic science. Liquid-phase chemiluminescence reagents such as tris(2,2'-bipyridyl)ruthenium(II) and acidic potassium permanganate exhibit remarkable sensitivity and complementary selectivity for many P. somniferum alkaloids, which has been exploited in the development of a range of analytical procedures using flow analysis, high-performance liquid chromatography, capillary electrophoresis and microfluidic instrumentation.

Determination of opiate alkaloids in process liquors using capillary electrophoresis.

This paper describes the determination of opiate alkaloids (morphine, codeine, oripavine and thebaine) in industrial process liquors using capillary zone electrophoresis with UV-absorption detection at 214 nm. A study of cyclodextrin type and concentration revealed that the addition of 30 mM hydroxypropyl-beta-cyclodextrin to the electrolyte solution (100mM Tris adjusted to pH 2.8) was suitable to resolve the four analytes of interest. Typical analysis time was 12 min and the limit of detection for each alkaloid was 2.5 x 10(-6) M. The results for the proposed methodology were in good agreement with those of a conventional HPLC procedure. Under the same conditions, short-end injection was used to reduce the effective separation length from 41.5 to 8.5 cm, which allowed the determination of morphine and thebaine in process liquors within 2.5 min.

Application of 2D-HPLC coupled with principal component analysis to study an industrial opiate processing stream.

Principal component analysis (PCA) loading plots were used to elucidate key differences between two-dimensional high performance liquid chromatography (2D-HPLC) fingerprint data from samples collected from stages along the Papaver somniferum industrial process chemistry workflow. Data reduction was completed using a 2D-HPLC peak picking approach as a precursor to chemometric analysis. Using comparisons of the final stages of product extraction as an example, PCA analysis of characteristic 2D-HPLC fingerprints accounted for 84.9% of variation between the two sample sets measured in triplicate, with 64.7% explained by PC1. Loadings plots of PC1 on each sample set identified where the significant changes were occurring and normalised bubble plots provided an indication of the relative importance of each of these changes. These findings highlight 2D-HPLC with appropriate chemometric analysis as a useful tool for the exploration of bioactive molecules within biomass.

Blind column selection protocol for two-dimensional high performance liquid chromatography.

The selection of two orthogonal columns for two-dimensional high performance liquid chromatography (LC×LC) separation of natural product extracts can be a labour intensive and time consuming process and in many cases is an entirely trial-and-error approach. This paper introduces a blind optimisation method for column selection of a black box of constituent components. A data processing pipeline, created in the open source application OpenMS®, was developed to map the components within the mixture of equal mass across a library of HPLC columns; LC×LC separation space utilisation was compared by measuring the fractional surface coverage, fcoverage. It was found that for a test mixture from an opium poppy (Papaver somniferum) extract, the combination of diphenyl and C18 stationary phases provided a predicted fcoverage of 0.48 and was matched with an actual usage of 0.43. OpenMS®, in conjunction with algorithms designed in house, have allowed for a significantly quicker selection of two orthogonal columns, which have been optimised for a LC×LC separation of crude extractions of plant material.

Rapid determination of Papaver somniferum alkaloids in process streams using monolithic column high-performance liquid chromatography with chemiluminescence detection.

We have combined high-performance liquid chromatography (HPLC) separations using a monolithic column with acidic potassium permanganate and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection in a rapid and highly sensitive method to monitor the process of extracting opiate alkaloids from Papaver somniferum. Due to the high flow rates allowed with the monolithic column and the inherent selectivity of the chemiluminescence reactions, the four predominant alkaloids--morphine, codeine, oripavine and thebaine--were determined in less than 2 min. The results obtained with numerous process samples compared favourable with those of the standard HPLC methodology. Limits of detection were 1x10(-10) M, 5x10(-10) M, 5x10(-10) M and 1x10(-9) M, for morphine, codeine, oripavine and thebaine, respectively.

Synthesis and preliminary analytical evaluation of the chemiluminescence from (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridyl)bis(2,2'-bipyridyl)ruthenium(II) covalently bonded to silica particles.

This paper describes, for the first time, a simple and effective synthetic route for covalently bonding the chemiluminescence reagent, (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridyl)bis(2,2'-bipyridyl)ruthenium(II) onto silica particles. The subsequent preparation of chemically regeneratable detection cells and their preliminary analytical evaluation with both sequential injection analysis and flow injection analysis are also reported. Unoptimised analytical figures of merit were established for standard solutions of codeine and sodium oxalate with detection limits calculated from three times the standard deviation of the blank signal, of 1 x 10(-8) M and 3 x 10(-7) M respectively. The chemically immobilised reagent exhibited some intriguing solvent and kinetic effects, which are also briefly discussed.