Degradation products determination

Specifications contain limits/require-ments for appearance and product description, identity testing, purity and impurity/ degradation products determination, quantity, and - in the case of biopharmaceuticals - mostly for potency. 

James, K. J., Crowley, J., Hamilton, B., Lehane, M., Skulberg, O., and Furey, A. (2005). Anatoxins and degradation products, determined using hybrid quadrupole time-of-flight and quadrupole ion-trap mass spectrometry forensic investigations of cyanobacterial neurotoxin poisoning. Rapid Commun. Mass Spectrom. 19, 1167-1175. 

James KJ, Crowley J, Hamilton B, Lehane M, Skulberg O, Furey A (2005) Anatoxins and degradation products, determined using hybrid quadrupole time-of-flight and quadrupole... 

The recent development and comparative application of modern separation techniques with regard to determination of alkylphosphonic acids and lewisite derivatives have been demonstrated. This report highlights advantages and shortcomings of GC equipped with mass spectrometry detector and HPLC as well as CE with UV-Vis detector. The comparison was made from the sampling point of view and separation/detection ability. The derivatization procedure for GC of main degradation products of nerve agents to determine in water samples was applied. Direct determination of lewisite derivatives by HPLC-UV was shown. Also optimization of indirect determination of alkylphosphonic acids in CE-UV was developed. Finally, the new instrumental development and future trends will be discussed. 

D. Barcelo and M. C. Hennion (Eds), Trace Determination of Pesticides and their Degradation Products in Water (Teclmiques and Instinmentation in Analytical Chemistry, Vol 19), Elsevier Oxford UK (1997). 

Determinations have been made of the solubility of lead linoleate prepared in the absence of oxygen and extracted with air-free water. Under these conditions, lead linoleate had a solubility of 0-002% at 25°C and the extract was corrosive when exposed to the air. When, however, the extraction was carried out in the presence of air, the resulting extract contained 0 07% solid material and was non-corrosive. It was concluded that in the presence of water and oxygen lead linoleate yielded soluble inhibitive degradation products. 

The quantification of kinins in human tissues or body fluids has been limited due to the inherent difficulties in accurately measuring the concentration of ephemeral peptides. Today HPLC-based and RIA/capture-ELA measurements are established to determine kinins in human plasma, liquor or mine. Serine protease inhibitors need to be added to prevent rapid degradation of the kinins in vitro during sample preparation. Kinins and their degradation products have been studied in various biological milieus such as plasma/ serum, urine, joint fluids, kidney, lung and skeletal muscle [2]. Under normal conditions, the concentration of kinins in these compartments is extremely low for... 

An enzyme immunoassay technique has been employed for measuring endosulfan and its degradation products (i.e., endosulfan diol, endosulfan sulfate, endosulfan ether, and endosulfan lactone) in water at 3 ppb (Chau and Terry 1972 Musial et al. 1976). However, this technique is not currently in use in environmental residue analysis. Further research into this technique could produce a rapid, rehable, and sensitive method for identifying contaminated areas posing a risk to human health. No additional methods for detecting endosulfan in environmental media appear to be necessary at this time. However, methods for the determination of endosulfan degradation products are needed. 

The objectives of the soil persistence experiments were (1) to learn the effect of soil type and concentration on the TCDD degradation rate, (2) to isolate and characterize degradation products from DCDD and TCDD, and (3) to determine whether chlorodioxins could be formed from chlorophenol condensation in the soil environment. This last study was essential since quality control at the manufacturing level could reduce or eliminate the formed dioxin impurity. But the biosynthesis of chlorodioxins by chlorophenol condensation in the soil environment could not be controlled and would have connotations for all chlorophenol-de-rived pesticides if formation did occur. The same question needed to be answered for photochemical condensation reactions leading to chloro-... 

Mangos, T.J. and Berger, R.G., Determination of major chlorophyll degradation products, Z. Lebensm. Unters. Forsh. A, 204, 345, 1997. 

For many situations, a simple total anthocyanin determination is inappropriate because of interference from polymeric anthocyanins, anthocyanin degradation products, or melanoidins from browning reactions. In those cases, the approach has been to measure the absorbance at two different pH values. The differential method measures the absorbance at two pH valnes and rehes on structural transformations of the anthocyanin chromophore as a function of pH. Anthocyanins switch from a saturated bright red-bluish color at pH 1 to colorless at pH 4.5. Conversely, polymeric anthocyanins and others retain their color at pH 4.5. Thus, measurement of anthocyanin samples at pH 1 and 4.5 can remove the interference of other materials that may show absorbance at the A is-max-... 

To determine whether the loss of vitamin Bjj in microwave-treated foods was dne to the conversion of vitamin Bjj to some inactive vitamin B,2 degradation prodncts, the hydroxocobalamin that predominates in food was treated by microwave heating for 6 min and then analyzed by TLC on sihca gel 60 with -bntanol/2-propanol/water (10 7 10, v/v) as a solvent. The treated hydroxocobalamin was separated into fonr red spots intact hydroxocobalamin remained at the origin (Fignre 10.5) [10]. These hydroxocobalamin degradation products were further purified to homogeneity by the nse of TLC and HPLC and characterized. 

Validation of true extraction efficiency normally requires the identification and quantitation of field-applied radiolabeled analyte(s), including resulting metabolites and all other degradation products. The manufacturer of a new pesticide has to perform such experiments and is able to determine the extraction efficiency of aged residues. Without any identification of residue components the calculation of the ratio between extracted radioactivity and total radioactivity inside the sample before extraction gives a first impression of the extraction efficiency of solvents. At best, this ratio is nearly 1 (i.e., a traceability of about 100%) and no further information is required. Such an efficient extraction solvent may serve as a reference solvent for any comparison with other extraction procedures. 

A monitoring system has been established to determine 90 pesticides including anilides and 10 related degradation products in river water. Pesticide residues in the water sample are collected on a PS-2 cartridge (265-mg) at a flow rate of 10 mL min, eluted with 3 mL of acetone, 3 mL of n-hexane and 3 mL of ethyl acetate successively, and determined by GC/MS. Overall recoveries ranged from 72 to 118%. Recoveries of mepronil, naproanilide, propanil and flutolanil at fortification levels of 0.1 and 2 mg kg Mn water by this method were 80-112%. The LODs were 0.01 -0.1 pg L ... 

Crescenzi et al. developed a multi-residue method for pesticides including propanil in drinking water, river water and groundwater based on SPE and LC/MS detection. The recoveries of the pesticides by this method were >80%. Santos etal. developed an on-line SPE method followed by LC/PAD and LC/MS detection in a simultaneous method for anilides and two degradation products (4-chloro-2-methylphenol and 2,4-dichlorophenol) of acidic herbicides in estuarine water samples. To determine the major degradation product of propanil, 3,4-dichloroaniline, the positive ion mode is needed for atmospheric pressure chemical ionization mass spectrometry (APCI/MS) detection. The LOD of 3,4-dichloroaniline by APCI/MS was 0.1-0.02 ng mL for 50-mL water samples. 

The complexity of the metabolism of alachlor, acetochlor, butachlor, and propachlor has led to the development of degradation methods capable of hydrolyzing the crop and animal product residues to readily quantitated degradation products. Alachlor and acetochlor metabolites can be hydrolyzed to two major classes of hydrolysis products, one which contains aniline with unsubstituted alkyl groups at the 2- and 6-positions, and the other which contains aniline with hydroxylation in the ring-attached ethyl group. For alachlor and acetochlor, the nonhydroxylated metabolites are hydrolyzed in base to 2,6-diethylaniline (DBA) and 2-ethyl-6-methylaniline (EMA), respectively, and hy-droxylated metabolites are hydrolyzed in base to 2-ethyl-6-(l-hydroxyethyl)aniline (HEEA) and 2-(l-hydroxyethyl)-6-methylaniline (HEMA), respectively. Butachlor is metabolized primarily to nonhydroxylated metabolites, which are hydrolyzed to DEA. Propachlor metabolites are hydrolyzed mainly to A-isopropylaniline (NIPA). The base hydrolysis products for each parent herbicide are shown in Eigure 1. Limited interference studies have been conducted with other herbicides such as metolachlor to confirm that its residues are not hydrolyzed to the EMA under the conditions used to determine acetochlor residues. Nonhydroxylated metabolites of alachlor and butachlor are both hydrolyzed to the same aniline, DEA, but these herbicides are not used on the same crops. 

The need to understand the fate of pesticides in the environment has necessitated the development of analytical methods for the determination of residues in environmental media. Adoption of methods utilizing instrumentation such as gas chro-matography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), liquid chromatography/tandem mass spectrometry (LC/MS/MS), or enzyme-linked immunosorbent assay (ELISA) has allowed the detection of minute amounts of pesticides and their degradation products in environmental samples. Sample preparation techniques such as solid-phase extraction (SPE), accelerated solvent extraction (ASE), or solid-phase microextraction (SPME) have also been important in the development of more reliable and sensitive analytical methods. 

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