Profenofos metabolites in human poisoning

Profenofos and its metabolites were determined in a case of fatal poisoning. Little profenofos and large amounts of metabolites were detected by gas chromatography/flame photometric detection in the acid extracts of blood and urine after methylation with diazomethane. Four major metabolites containing phosphorus were identified with the synthesized metabolites, namely, despropylated profenofos, desethylated profenofos and des-S-propylated profenofos, respectively. 4-Bromo-2-chlorophenol (BCP), an aryl moiety of profenofos, was also determined in blood and urine with high performance liquid chromatograph (HPLC) as free or conjugated metabolites.     

Sex determination and estimation of stature from the long bones of the arm

The determination of sex and the estimation of stature from bones play an important role in identifying unknown bodies, parts of bodies or skeletal remains. In medico-legal practice statements on the probable sex of a decomposed body or part of a body are often expected even during autopsy. The present study was, therefore, restricted to few easily accessible dimensions from bones which were prepared only by mechanically removing soft tissues, tendons and ligaments. The specimens came from the Anatomical Institutes in Munich and Cologne from the years 1994-1998 including a total of 143 individuals (64 males and 79 females). The mean age was 79 years (46-108), the mean body height 161cm (134-189). The following measurements were taken: maximum humeral length (mean: 33.4cm in males; 30.7cm in females), vertical humeral head diameter (mean: 5.0cm in males, 4.4cm in females), humeral epicondylar width (mean: 6.6cm in males; 5.8cm in females), maximum ulnar length (mean: 26.5cm in males, 23.8cm in females), proximal ulnar width (mean: 3.4cm in males, 2.9cm in females), distal ulnar width (mean: 2.2cm in males; 1.8cm in females), maximum radial length (mean: 24.6cm in males; 22.0cm in females), radial head diameter (mean: 2.6cm in males, 2.2cm in females) and distal radial width (mean: 3.6cm in males; 3.2cm in females). The differences between the means in males and females were significant (P<0.0005). A discriminant analysis was carried out with good results. A percentage of 94.93% of cases were correctly classified when all measures of the radius were applied jointly, followed by humerus (93.15%) and ulna (90.58%). Applied singly, the humeral head diameter allowed the best distinction (90.41% correctly grouped cases), followed by the radial length (89.13%), the radial head diameter (88.57%) and the humeral epicondylar width (88.49%). The linear regression analysis for quantifying the correlation between the bone lengths and the stature led to unsatifactory results with large 95%-confidence intervals for the coefficients and high standard errors of estimate.     

Cranio-facial morphanalysis: a new method for enhancing reliability while identifying skulls by photo superimposition

Skull-photograph superimposition continues to be the most prevalent method employed for identifying a skull recovered in a criminal case as that belonging to a putative victim whose face photograph is available. The reliability of identification achieved has been shown to be 91%, indicating the possibility of a skull mismatching with a face photograph belonging to a person other than the actual deceased. This lack of reliability dampens the confidence of the expert and in turn confounds the mind of the judge. It has been shown that the variations in the shape of the facial organs are influenced by the corresponding variations in the skeletal elements of the facial skull. "Cranio-facial morphanalysis", a new anthroposcopic method proposed here for evaluating the shape correlations between a skull and a face photograph, when applied conjointly with skull-photograph superimposition is shown to increase the reliability in forensic skull identification.     

The effect of metal salt treatment on the photoluminescence of DFO-treated fingerprints

Ninhydrin developed fingerprints can be enhanced by treatment with a zinc or cadmium salt. The resulting fingerprint luminescence has been attributed to the induced coplanarity of the bicyclic indanedione rings of Ruhemann's purple due to complexation with the metal ions. This paper explores whether this effect also occurs in the 1,8-diaza-9-fluorenone (DFO)-amino acid adduct (1), formed from the reaction of DFO with amino acids. Molecular modeling studies of (1) indicate a relatively small out-of-plane angle of 24 degrees. 1H NMR studies indicate (1) is asymmetric about the C2 axis in contrast to what has been previously reported. Little, if any, enhancement of luminescence was observed with Zn, Cd, Ru or Eu treated DFO developed latent fingerprints. This lack of enhancement was also borne out by solution luminescence studies. Given this lack of enhancement of luminescence, solutions of (1) and the four metal ions above were analyzed by electrospray mass spectrometry (ESMS). This indicated the formation of predominantly 1:1 complexes of (1) with both Zn and Cd, and the 2:1 complex with ruthenium. No evidence of a Eu complex was found by ESMS.     

Colchicine poisoning: case report of two homicides

Deaths resulting from the oral ingestion of colchicine are occasionally associated with suicides and therapeutic toxicity. However, homicidal deaths in which this drug is used are extremely rare. Two homicides in which colchicine was used are reported.     

Sensitive and specific multiresidue methods for the determination of pesticides of various classes in clinical and forensic toxicology

Original and sensitive multiresidue methods are presented for the detection and quantitation, in human biological matrices, of 61 pesticides of toxicological significance in human. These methods involved rapid solid-phase extraction using new polymeric support (HLB and MCX) OASIS cartridges. Gas chromatography-mass spectrometry (GC-MS) was used for volatile (organophosphate, organochlorine, phtalimide, uracil) pesticides and liquid chromatography-ionspray-mass spectrometry (LC-MS) for thermolabile and polar pesticides (carbamates, benzimidazoles). Acquisition was performed in the selected ion monitoring (SIM) mode. Extraction recovery varied owing to the nature of pesticides, but was satisfactory for all. Limits of detection (LODs) and limits of quantitation (LOQs) ranged, respectively, from 2.5 to 20 and from 5 to 50ng/ml. An excellent linearity was observed from LOQs up to 1000ng/ml for all the pesticides studied. The proposed procedures yielded reproducible results with good inter-assay accuracy and precision. A few cases of intoxication are presented to demonstrate the diagnostic interest of these methods: in two cases were determined lethal concentrations of endosulfan and carbofuran; in four other cases, the procedures helped diagnose intoxication with, respectively, parathion-ethyl, the association of bromacil and strychnine, bifenthrin and aldicarb.     

Spectra interference between diquat and paraquat by second derivative spectrophotometry

A rapid and accurate method, combining solid-phase extraction and second-order derivative spectrophotomety approaches, is developed for the simultaneous determination of diquat (DQ) and paraquat (PQ) in blood, tissue and urine samples. Supernatant resulting from the precipitation of protein (with trichloroacetic acid) in plasma and tissue or Amberlite IRA-401 resin treated urine are passed through a mini-column packed with Wakogel gel (Silica gel). Analytes are then eluted with a non-organic solvent, 0.2mol/l HCl solution containing 2mol/l NH(4)Cl. UV spectrum of the eluent in 220-350nm range provides effective screen to detect the presence of DQ and/or PQ. In the presence of DQ or PQ alone, the analyte present is quantitated by conventional zero- or second-order derivative spectrophotometry. The calibration curve in the 0.1-5.0mg/l range for either analyte obeys Beer's law. When both DQ and PQ are present, their concentrations are determined by the peak amplitudes of their respective second-derivative spectra after the addition of alkaline dithionite reagent. Interference is negligible when the DQ/PQ concentration ratio is within the 5.0-0.2 range.Using a 2-ml of sample size, the detection limits for DQ and PQ in plasma are 0.02 and 0.005mg/l. The corresponding detection limits for urine samples (10ml sample size) are 0.004 and 0.001mg/l. Recoveries of DQ and PQ in triplicate plasma and urine samples spiked with 0.5mg/l of analytes are 93 and 85%. The precision of the proposed method resulting from triplicate study of spiked urine samples varies from 3.2 to 4.6% at 0.5mg/l of DQ and PQ, respectively.     

Detection and assay of cis- and trans-isomers of 4-methylaminorex in urine, plasma and tissue samples

The 4-methylaminorex (4-MAX) is an amphetamine-related psychostimulant drug that has appeared on the clandestine market with a street name of "U4Euh". This compound exists as four stereoisomers, trans-4R,5R, trans-4S,5S, cis-4R,5S and cis-4S,5R, of which the cis forms have been classified as Schedule I substances in the US. The increasing variety of designer drugs has highlighted the importance of detection, identification, and quantitative measurement of these drugs, including 4-MAX, in biological samples. In the present study, the isomers of 4-MAX were detected in urine of rats treated with the drugs by some but not all of the on-site immunoassays tested, mainly as amphetamine or methamphetamine. To facilitate identification of 4-MAX by laboratories specialized in drug analysis, the electron-ionization mass spectrum and TLC data for underivatized 4-MAX using a routine laboratory drug-screening procedure is provided. In addition, a GC/MS method is described for the quantitative determination of cis- and trans-4-MAX as tert-butyldimethylsilyl-derivatives in plasma, urine and tissue.