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The primary objective of this review is to provide a comprehensive overview of the challenges involved in detecting ancient ayahuasca, a traditional hallucinogenic drink from the Amazon region, which is prepared using Banisteriopsis caapi... more
The primary objective of this review is to provide a comprehensive overview of the challenges involved in detecting ancient ayahuasca, a traditional hallucinogenic drink from the Amazon region, which is prepared using Banisteriopsis caapi liana and other plants, by utilizing advanced analytical techniques. The presence of harmine and harmaline in Andean archaeological findings has led certain authors to speculate that the Banisteriopsis liana may have been the source plant responsible for their occurrence. Consequently, the utilization of this liana can be traced back to at least 500 CE. However, a combination of archaeological, ethnobotanical, biochemical and analytical chemistry considerations has rendered uncertain the true origins of the presence of harmine and harmaline in ancient mummies and artifacts. Thus, the archaeological evidence does not convincingly prove the ancient usage of ayahuasca.
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ABSTRACT In contrast to GC–MS, many factors are influencing mass spectra of organic compounds when analyzed by LC–MS. In-source or transport collision-induced dissociation by electrospray ionization or atmospheric pressure chemical... more
ABSTRACT In contrast to GC–MS, many factors are influencing mass spectra of organic compounds when analyzed by LC–MS. In-source or transport collision-induced dissociation by electrospray ionization or atmospheric pressure chemical ionization demonstrate the need for experimental condition standardization when building-up a library of reference spectra. Magnetic sector, quadrupole, ion trap or time-of-flight filters placed on single or multiple mass spectrometry instruments coupled with HPLC deliver unique mass intensities pattern from the same molecules that are most often not readily comparable between each other. This makes it very difficult or even impossible to rely on any collections of reference data whatever comparison algorithm is applied for library search or manual comparison when full confirmation of identity is required. Typical areas of expertise are very sensitive to sound and complete package procedures to withstand administrative or court’s scrutiny. In this paper, this problem is referred to the specific field of forensic toxicology and doping control in sports. Several official guidelines have been released recently and await confrontation with concrete cases. Closely related areas like residues in living animals and meat products are regulating these aspects with detailed procedures. Basically, they all propose the accumulation of a finite quantity of information about the unknown molecule and the reference substance. These confirmatory packages are briefly exposed, compared and evaluated for their future application to the newest LC–MS techniques that are more frequently used within these critical fields of expertise.
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Quantitative analysis of indolyl-3-acetic acid (IAA) in different parts of maize root tips (Zea mays L. cv. Kelvedon 33) were performed by selective ion current monitoring detection (or mass fragmentography). It was found that the cap... more
Quantitative analysis of indolyl-3-acetic acid (IAA) in different parts of maize root tips (Zea mays L. cv. Kelvedon 33) were performed by selective ion current monitoring detection (or mass fragmentography). It was found that the cap contained 356.6±16.2 μg of IAA kg(-1) fresh weight; the apex had only half this concentration of IAA. Calculations indicated that the 10-mm apical segments of the root contained 109.6 μg kg(-1) fresh weight. The possibility that the growth regulator formed in the cap and inhibiting the elongation of the extension zone of the root is IAA is discussed.
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Studies on phototropism and gravitropism at the beginning of this century led to the discovery of the diffusible growth promoting factor from coleoptile tips [41], later called “auxin” [14]. Indole-3-acetic acid (IAA) has been shown to be... more
Studies on phototropism and gravitropism at the beginning of this century led to the discovery of the diffusible growth promoting factor from coleoptile tips [41], later called “auxin” [14]. Indole-3-acetic acid (IAA) has been shown to be one of the main auxins [11], and is known to be present in most of higher plants. This natural hormone appears to be an important endogenous regulator controlling cell enlargement and division, and could be implicated in gravireaction processes [5]. Extensive coverage of the occurrence, biochemistry and physiology of IAA and related auxins were recently published [6, 16, 18, 35].
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The actual antidoping control rules applied in sports (as established by the International Olympic Committee and the International Sport Federations) state that a positive case is chemically established by the unequivocal detection of a... more
The actual antidoping control rules applied in sports (as established by the International Olympic Committee and the International Sport Federations) state that a positive case is chemically established by the unequivocal detection of a forbidden parent molecule and/or any of its metabolite(s) in urine, no matter the amounts which were administered and when the drug was taken. Screening is accomplished most of the time by using GC-MS procedures. These have been optimized to detect most if not all of the forbidden compounds which are put on a list. Recently, attempts have been made on scalp hair to demonstrate the value of this matrix as a possible means for differentiating between therapeutic use and doping abuse. In particular, GC-mass selective detector and GC-high resolution MS were successfully applied to treated animals and body-builders for anabolic agents (steroids and beta-2-agonists) at high sensitivity detection (low ng/g level). Naturally occurring molecules, like testosterone and its metabolites, could also be differentiated from their synthetic counterparts. Positive cases are more often challenged in courts and retrospectivity in time of the drug(s) intake is becoming an important issue for evaluating the responsibility of the person. This is can be based on hair analyses if the drugs have been taken at regular intervals. Stimulants and narcotics are often used in sports like drug of abuse in the ordinary social contexts. On the other hand, anabolic agents, when taken to improve the physical performances, follow complex regimens with the mixing of various formulas and dosages. Scalp hair references ranges for these as well as for endogenous substances still wait to be established statistically for competing, well-trained athletes. The incorporation rate into blond or gray hair is poorer than that of dark colored hair raising the question of individuals equality against the controls, a very important matter of concern for the sport's governing bodies. The frequency of hair cutting and short hair cuts necessary to gain speed in specific sports like swimming are other critical factors. On the other hands, irregular hair growth, associated with the washout effect through multiple washing and staining processes over expanded time intervals can cause concentrating or diluting effects. So far, a minority of prohibited substances could be detected in scalp hair with the sensitivity and specificity required in the context of the sport's activities. From the above, clear limitations of the usefulness of hair analysis in doping control analysis are obvious until a lot more data relevant to this particular field have been collected.
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AbstractPeptide hormones have been abused in sports to improve physical performances since recombinant products which are the exact replicate of their natural models became available. Both human growth hormone and erythropoietin are now... more
AbstractPeptide hormones have been abused in sports to improve physical performances since recombinant products which are the exact replicate of their natural models became available. Both human growth hormone and erythropoietin are now available in large quantities on the unofficial market for those who want to use them for applications lying outside the accepted medical applications Such abuse calls for strict controls, because non-medical abuses of these powerful products can produce dangerous side-effects. The duration time of both peptides in the body is so short that direct detection of the recombinant products is impossible. The actual tests available for their detection rely on immunological assays which are not considered good enough for determining their abuse in sports. All possible secondary markers are now being sought for adoption as a screening test which still requires confirmation by the direct measurement of the hormones themselves. Blood samples might well appear to be more useful for t...
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A powder prepared by Haitian voodoo sorcerers for the making of zombis was extracted with acetic acid, the extract concentrated and applied to a small cation exchange column followed by elution with water and then acetic acid. The water... more
A powder prepared by Haitian voodoo sorcerers for the making of zombis was extracted with acetic acid, the extract concentrated and applied to a small cation exchange column followed by elution with water and then acetic acid. The water and acetic acid eluents were analysed by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry. The analyses indicated the presence of an alkaline degradation product of tetrodotoxin, namely 2-amino-6-hydroxymethyl-8-hydroxyquinazoline, after base treatment, and of tetrodotoxin and an isomer on direct thermospray mass spectral activity.
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Forensic scientists have long detected the presence of drugs and their metabolites in biological materials using body fluids such as urine, blood and/or other biological liquids or tissues. For doping analysis, only urine has so far been... more
Forensic scientists have long detected the presence of drugs and their metabolites in biological materials using body fluids such as urine, blood and/or other biological liquids or tissues. For doping analysis, only urine has so far been collected. In recent years, remarkable advances in sensitive analytical techniques have encouraged the analysis of drugs in unconventional biological samples such as hair, saliva and sweat. These samples are easily collected, although drug levels are often lower than the corresponding levels in urine or blood. This chapter reviews recent studies in the detection of doping agents in hair, saliva and sweat. Sampling, analytical procedures and interpretation of the results are discussed in comparison with those obtained from urine and blood samples.
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Several solvents were tested for the extraction of the alkaloids in Erythroxylum coca. The resulting crude extracts were analyzed by gas chromatography--mass spectrometry. Ethanol extraction was found to be the only quantitative method... more
Several solvents were tested for the extraction of the alkaloids in Erythroxylum coca. The resulting crude extracts were analyzed by gas chromatography--mass spectrometry. Ethanol extraction was found to be the only quantitative method presenting no artifacts. It was established that cocaine and cis- and trans-cinnamoylcocaine were the endogenous alkaloids in E. coca leaves. From the several breakdown compounds arising during long-term extraction with H2SO4 or CHCl3, ecgonine methyl ester was the only alkaloid fully identified; ecgonine methyl ester was tentatively identified on the basis of its mass spectrum fragmentation pattern. Quantification by mass fragmentography of the three endogenous compounds was performed using a stable-isotope dilution technique on individual leaves of single branches of E. coca, E. novogranatense and E. novogranatense var. truxillense. The relative amounts of these alkaloids changed with leaf age as well as between species and varieties. The variation in alkaloid levels between individual leaves was too great to allow the use of the ratio between cocaine and the cinnamoylcocaine levels as a taxonomic marker. The initial pH value of 17 different alkaline substances traditionally used during coca leaf chewing was measured after dissolution in H2O; values ranged between 10.1 and 12.8. Buffer capacity was determined by titration with HCl. Three types of curve shapes were obtained which could correspond to NaOH, Na2CO3 and NaHCO3 titration curves. One sample of alkaline material had no buffer capacity at all. The recovery and breakdown of the cocaine contained in E. coca leaf power was monitored for one hour at various pHs at 37 degrees C. The levels of cocaine and benzoylecgonine did not change by more than 17% at any of the pHs tested (6.0, 9.0 and 11.5). It was concluded that the alkaline substances are mainly responsible for the transformation of the alkaloids to free bases and not for a major hydrolysis of cocaine.
Research Interests: Chemistry, Complementary and Alternative Medicine, Chromatography, Plant Biology, Biology, and 13 moreEthnopharmacology, Medicinal Plants, Medicine, Humans, Coca, Alkaloids, Plant extracts, medicinal & Aromatic plants, Mastication, Gas Chromatography/mass Spectrometry, Alkaloid, Alkalies, and Pharmacology and pharmaceutical sciences
The frequent lack of correlation between endogenous levels of auxins and selected physiological processes which has often been reported in the literature suggests the conclusion that such correlations do not often exist. However, from a... more
The frequent lack of correlation between endogenous levels of auxins and selected physiological processes which has often been reported in the literature suggests the conclusion that such correlations do not often exist. However, from a critical evaluation of the methods used for such studies, it is apparent that most of the qualitative and quantitative determinations made for auxins in general did not comply with good analytical practice. For example, some mass spectra (MS) of both reference and putative IAA derivatives that have been recently published in the literature contain gross errors (i.e., Arteca et al. 1980). In addition, many of the quantitative calculations have been based on nonspecific ions or detector signals.
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Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum... more
Furosemide (FD: Lasix) is a loop diuretic which strongly increases both urine flow and electrolyte urinary excretion. Healthy volunteers were administered 40 mg orally (dissolved in water) and concentrations of FD were determined in serum and urine for up to 6 h for eight subjects, who absorbed water at a rate of 400 ml/h. Quantification was performed by HPLC with fluorescence detection (excitation at 233 nm, emission at 389 nm) with a limit of detection of 5 ng/ml for a 300-microliters sample. The elution of FD was completed within 4 min using a gradient of acetonitrile concentration rising from 30 to 50% in 0.08 M phosphoric acid. The delay to the peak serum concentration ranged from 60 to 120 min. FD was still easily measurable in the sera from all subjects 6 h after administration. In urine, the excretion rates reached their maximum between 1 and 3 h. The total amount of FD excreted in the urine averaged 11.2 mg (range 7.6-14.0 mg), with a mean urine volume of 3024 ml (range 2620-3596 ml). Moreover, the urine density was lower than 1.010 (recommended as an upper limit in doping analysis to screen diuretics) only for 2 h. An additional volunteer was administered 40 mg of FD and his urine was collected over a longer period. FD was still detectable 48 h after intake. Gas chromatography-mass spectrometry with different types of ionization was used to confirm the occurrence of FD after permethylation of the extract. Negative-ion chemical ionization, with ammonia as reactant gas, was found to be the most sensitive method of detection.
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Abstract An ABA pretreatment enhanced the geotropism of maize (cv. LG 11) root segments. Such stimulation was much stronger for georeacting roots in darkness. When ABA was applied asymmetrically on the lower part of the applical cut end... more
Abstract An ABA pretreatment enhanced the geotropism of maize (cv. LG 11) root segments. Such stimulation was much stronger for georeacting roots in darkness. When ABA was applied asymmetrically on the lower part of the applical cut end of decapped segments, it induced a downward curvature which increased with increasing ABA concentration. Using the GC/MS technique, ABA was found in the root tip: the light exposed roots containing more ABA than those kept in darkness. But no changes in the total ABA level were obtained between vertical and horizontal segments. This indicates that the increase in the growth inhibitor amount in the lower part of the growing root zone - which could explain the positive root geotropism - has to be related to a concomitant decrease in their level in the upper part of this zone, with a total concentration being constant.
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Research Interests: Chemistry, Analytical Chemistry, Electrochemistry, Medicine, Analytical Toxicology, and 10 moreAnalytical, Hallucinogens, Ecstasy, High Pressure Liquid Chromatography, Tablets, Gas Chromatography/mass Spectrometry, Street Drugs, Psychotropic Drugs, designer drug, and Pharmacology and pharmaceutical sciences
In March 1995, a decision about cultivation of cannabis was issued by the Swiss Federal Offices of Public Health, Police and Agriculture in order to satisfy the growing interest of farmers and other people in hemp farming. It pointed out... more
In March 1995, a decision about cultivation of cannabis was issued by the Swiss Federal Offices of Public Health, Police and Agriculture in order to satisfy the growing interest of farmers and other people in hemp farming. It pointed out that 1)... each hemp plant contains THC and must be therefore considered a drug, 2)... no permission is required for those who grow hemp without the intention to produce drugs ... meaning that the choice of the plant variety was not restricted to those which are characterized by a low THC concentration and grown in a few countries belonging to the European Union. Claiming that natural hemp must contain significant amounts of THC and thanks to the Swiss legislation, areas dedicated to hemp cultivation develop considerably. Most hemp plants which are submitted to our laboratories by the police for THC quantification belong to the drug-type. Nowadays, a great deal of goods (food and beverages, cosmetics, drugs) made of hemp are marketed in Switzerland. Strong suspicions exist however that several of these products could be used as a screen for the illegal market of cannabis. For instance, despite financial support from the state, fiber hemp cultivation remains unsuccessful. No advantage with regard to seed productivity, edible seed and essential oils qualities and yields have been found for drug hemp over fiber hemp by agricultural research stations up to now. Several clues about the possible illicit use of hemp goods rich in THC, especially hemp tea made of flower tops and "therapeutic" pillows filled with cannabis exist. Recently, two Federal edits were issued in order to restrict the selling of hemp seedlings and of hemp foods and beverages to those containing only low amounts of THC. However, the marketing of hemp plants used for decorating remains free partly explaining the recent success of these "beautiful" plants. Broadly speaking, the Swiss and European legislations about hemp have approached mutually during the last years.
Research Interests: Business, Praxis, Agriculture, Medicine, Humans, and 6 moreLegislation, Pubmed, Switzerland, Cannabis, Cannabis Sativa, and Dronabinol
Two methods, capillary electrophoresis (CE) and liquid chromatography (LC), have been developed for the separation and quantitation of amphetamines found in illicit drug seizures. These methods allowed us to determine, within less than 8... more
Two methods, capillary electrophoresis (CE) and liquid chromatography (LC), have been developed for the separation and quantitation of amphetamines found in illicit drug seizures. These methods allowed us to determine, within less than 8 min and without interference from adulterants, the presence of six current amphetamines. No significant statistical differences between both validated methods were observed as linearity, precision, accuracy
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ABSTRACT The Swiss German chapter of the Exit Association provides conditional assistance to individuals wishing to end their own lives. The Exit Association advocates death with dignity and fights for the right to freely choose the... more
ABSTRACT The Swiss German chapter of the Exit Association provides conditional assistance to individuals wishing to end their own lives. The Exit Association advocates death with dignity and fights for the right to freely choose the timing of one's own death. According to the Swiss criminal code (articles 114 and 115), altruistic assistance to suicide is not punishable. Active euthanasia is punished by imprisonment. An individual commits active euthanasia if he or she is driven by honorable motives (e.g., pity) and causes the death of another person wishing to die who seriously and insistently requests such action. Based on our information, the preparation for suicide and its completion relies on a well-defined protocol. First, the candidate's eligibility for Exit Association assistance is verified. The candidate then writes a farewell declaration that explicitly confirms the will to terminate his or her own life. A written report describes the events during the suicide procedure. Depending on the circumstances, the investigative judge requests a forensic autopsy and toxicologic analyses. The results of the forensic investigations conducted in the cases presented here are in agreement with the scenario described in the reports of the Exit Association, namely, suicide by massive ingestion of pentobarbital.
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Epidemiological and analytical laboratory records concerning living drivers suspected of driving under the influence of drug (DUID) during the 13 years period ranging from 1982 to 1994 were examined. This study included 641 records. 551... more
Epidemiological and analytical laboratory records concerning living drivers suspected of driving under the influence of drug (DUID) during the 13 years period ranging from 1982 to 1994 were examined. This study included 641 records. 551 men (86%) and 90 women (14%). The average age of the drivers was 27 +/- 7 years (n = 636, minimum 18 and maximum 74) and the 18-30 interval age range was overrepresented (80%) in this population sample. A traffic accident had occurred in 254 (40%) of the records, 273 (43%) drivers were suspected of DUID during police controls and 95 (15%) drivers were suspected of DUID because of their erratic driving. One or more psychoactive drugs were found in 92.8% of the samples. In these records, cannabinoids were found in 57%, opiates in 36%, ethanol in 36%, benzodiazepines in 15%, cocaine in 11%, methadone in 10% and amphetamines in 4%. The majority (58%) of cases presented two or more drugs in biological samples, thus indicating a high incidence of potential interactions between drugs. This observation was specially relevant for methadone and methaqualone. We conclude that police suspicion about drivers under influence highly correlated with positive results for drug analyses in biological samples.
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Abstract An ABA pretreatment enhanced the geotropism of maize (cv. LG 11) root segments. Such stimulation was much stronger for georeacting roots in darkness. When ABA was applied asymmetrically on the lower part of the applical cut end... more
Abstract An ABA pretreatment enhanced the geotropism of maize (cv. LG 11) root segments. Such stimulation was much stronger for georeacting roots in darkness. When ABA was applied asymmetrically on the lower part of the applical cut end of decapped segments, it induced a downward curvature which increased with increasing ABA concentration. Using the GC/MS technique, ABA was found in the root tip: the light exposed roots containing more ABA than those kept in darkness. But no changes in the total ABA level were obtained between vertical and horizontal segments. This indicates that the increase in the growth inhibitor amount in the lower part of the growing root zone - which could explain the positive root geotropism - has to be related to a concomitant decrease in their level in the upper part of this zone, with a total concentration being constant.
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A recent retrospective epidemiological study carried out in the canton de Vaud (Switzerland) concerning drivers suspected of driving under the influence of drugs (DUID) showed a high incidence of cases containing two and more drugs. The... more
A recent retrospective epidemiological study carried out in the canton de Vaud (Switzerland) concerning drivers suspected of driving under the influence of drugs (DUID) showed a high incidence of cases containing two and more drugs. The declarations of the drivers and the observations of the police were necessary for later interpretation but not sufficient to justify a simplified analytical screening procedure. A forensic analytical strategy was developed for analysis of a large variety of drugs in urine and/or whole blood. The analytical strategy included screening, confirmation and quantitation of drugs. If screening was preferably performed in urine, confirmation and quantitation analysis were done in blood, in order to give useful results for forensic interpretation and the possibility to try to answer whether or not the driver was under the influence of drugs. Immunological tests and gas-chromatography coupled with mass-spectrometry (GC-MS) were used for screening. All identifications and confirmations were performed by GC-MS. Amphetamines, opiates, cocaine and cannabinoids were quantified by GC-MS after derivatization, using deuterium labeled internal standards. Other drugs were quantified by GC-NPD, GC-ECD or HPLC-UV. Quantitation of ethanol was performed by two different chromatographic methods. (A) For the covering abstract see IRRD 893732.
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This report presents the different strategies for identifying heroin users. The criteria allowing a clear distinction between an abuse of heroin and a lawful consumption of opiates are deeply discussed. Reliable and sensitive analytical... more
This report presents the different strategies for identifying heroin users. The criteria allowing a clear distinction between an abuse of heroin and a lawful consumption of opiates are deeply discussed. Reliable and sensitive analytical methods are now available for forensic opiate testing. The detection of 6-mono-acetylmorphine (MAM) indicates that heroin was administered within 24 hours or less of specimen collection. In the absence of MAM or after consumption of several opiates, the relative ratios of morphine, codeine and eventually ethylmorphine must be known in order to determine which opiate(s) was (were) taken. A total amount of opiates of less than 0.3 mg/l very often precludes any characterization of the ingested drug(s). Here we have to point out that forensic opiate testing should be done carefully. Interpretation of results requires more than detection of opiates or morphine alone, irrespective of the number of techniques used.
Research Interests: Medicine, Forensic Toxicology, Pubmed, Morphine, Heroin, and 3 morePraxis Philosophy, Codeine, and Opiate
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Preamble During the 20 th century, a multi-million dollar horse racing industry had developed. For competitions two main elements must be considered when controlling of drugs in racehorses : 1. Legitimate treatment, supervised by a... more
Preamble During the 20 th century, a multi-million dollar horse racing industry had developed. For competitions two main elements must be considered when controlling of drugs in racehorses : 1. Legitimate treatment, supervised by a veterinarian, may be underway for illness or injury so that the horse may be fit to perform. Drugs may have been administered to the horse with the intend of altering the performance. This is obtained by analysing official test samples (urine and/or blood) which are taken before and/or after competition. In some countries, between competition testing is also organised. Treated horses have to be restrained from racing until they have eliminated any traces of the administered substances and/or their metabolites. This dual nature of therapeutic medication and drug abuse in racehorses created a difficult regulatory problem. The act of taking substances which are influencing the physical performance and are usually banned is now known as doping. Most racing jurisdictions have strict medication rules, similar to the control of drugs in human athletes, which prohibit the presence of any drug in an official test sample of urine, blood or other body fluids taken before or after the race. The most recent rules of the majority of governing bodies for horse sport conform roughly to those of the " Fédération Equestre Internationale " (FEI). Similar rules are adopted by the International Federation of Horseracing Authorities (IFHA). These two bodies are the leading international equestrian sports' associations. These regulations consist in forbidden the presence of any substances in the body of the animal. The stated objective of such regulations is to protect a fair competition or more specifically, any bettor from wagering on horses of unknown or inconsistent performance owing to the influence of drugs. Racing analysts and veterinarians are the forensic and sport medicine experts who are responsible for monitoring the medication of competing horses. The prime responsibility of racing laboratories is to protect the integrity of racing together with racing authorities. Context of controlling Owing to the proliferation of pharmaceuticals in the last 40 years, it has come difficult for the analyst to keep with new drug developments. Even before new pharmacologically active substances are introduced on the market, whether for human or veterinary uses, they may appear in samples taken during doping controls. Comparing the work of the scientist who has to analyse urine and/or blood samples from competing horses with analysts dealing with clinical, toxicological or forensic samples shows obvious differences. In sport, the laboratory receives coded samples, with the only indication of the type of horse. No additional information is given, one is not provided with a case report, nor advised to look for any particular class of drug because of any evidence such as apparent intoxication. If a doping agent has been taken, the amount in blood is likely to be within the normal that is the therapeutic range of concentration. Obviously, we never encounter any drug overdose case where large concentrations of the drug and/or metabolites are typically to be present. A limited volume of urine or blood is provided, typically between 40 and 50 ml, and, for the large majority of the cases, it will be no opportunity for a second follow-up sample. Nevertheless, the exact identity of any banned substance present in the sample must be made unequivocally and frequently within strict time limits of, usually between 3 and 10 days, as specified in the contract agreed with the controlling authorities.
