首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Abstract: Crystal violet is a very common dye in ballpoint ink. Recent research suggests that the degradation of triarylmethane dyes gives an indication of the age of a ballpoint pen entry on a document. The main problem for the quantitative evaluation of the degradation is that it is highly dependent on the exposure to light. Moreover additional factors, such as additives and substrate play an important role in this process. The aim of this work is to compare the degradation pathways of the pure dye in water and ethanol upon exposure to xenon light by UV/VIS spectrophotometry and laser desorption ionization. Significant differences have been observed in the products and the kinetics of the degradation. N-demethylation, an expected decomposition process, was found to take place only in aqueous solution and kinetics calculations showed that the degradation occurred 2.5 times faster in ethanol compared to water. The degradation of crystal violet in inks from four ballpoint pens on paper was also studied for entries made over 2–3 years. It was observed that degradation reactions were quenched by the presence of another dye due to competitive absorption. It was also observed that the thickness of a stroke (concentration of ink) influenced the degradation process. In the absence of light only one ballpoint pen showed slight degradation. A better understanding of the influence of the paper, ink composition, and storage conditions is necessary to interpret correctly the age of an ink based on the degradation of dyes.  相似文献   

2.
目的 探究死后血浆和溶血样本中免疫球蛋白E(immunoglobulin E,IgE)经过不同保存条件及冻融处理后的稳定性.方法 选取39例死后48 h内非冷冻尸体的心血样本,其中20例取血浆样本,19例取全血制成溶血样本.将样本置于-20℃、4℃、25℃条件下保存28 d及-80℃条件下保存1年以探究IgE在不同保存...  相似文献   

3.
Abstract: Human scent evidence collected from objects at a crime scene is used for scent discrimination with specially trained canines. Storage of the scent evidence is usually required yet no optimized storage protocol has been determined. Storage containers including glass, polyethylene, and aluminized pouches were evaluated to determine the optimal medium for storing human scent evidence of which glass was determined to be the optimal storage matrix. Hand odor samples were collected on three different sorbent materials, sealed in glass vials and subjected to different storage environments including room temperature, ?80°C conditions, dark storage, and UVA/UVB light exposure over a 7‐week period. Volatile organic compounds (VOCs) in the headspace of the samples were extracted and identified using solid‐phase micro‐extraction–gas chromatography/mass spectrometry (SPME–GC/MS). Three‐dimensional covariance mapping showed that glass containers subjected to minimal UVA/UVB light exposure provide the most stable environment for stored human scent samples.  相似文献   

4.
Cholesterol and squalene are fatty materials of latent fingermarks that can be utilized for dating methodologies and visualization techniques. Previous studies have suggested these compounds undergo degradation in fingermarks as a function of time (days) and light at ambient temperature. However, studies assessing how their composition changes at low and high temperatures over short periods of time (hours) have not been published previously. Here, we performed quantitative analysis of cholesterol and squalene in natural fingermark residue using PVDF membrane, after exposure to a range of temperatures (−20 to 100°C) for 4 and 8 h. We found that levels of both fatty materials remained constant at −20 to 60°C, but both showed significant reduction at 100°C, over short exposure times. These results indicate that cholesterol and squalene are detectable at −20 to 60°C, whereas at 100°C or higher, both are lost due to rapid thermal degradation.  相似文献   

5.
Analogs of methcathinone (MC), a psychoactive stimulant, are in circulation all over the world. These analogs have been assumed to be unstable in alkaline solutions, as is MC itself. The aims of this study were: (i) to identify the degradation products of 4-methylmethcathinone (4-MMC), a typical MC analog, in solution at pH 12 and to determine the degradation pathway, (ii) to investigate the effects of antioxidants such as l-ascorbic acid and sodium sulfite on the degradation of 4-MMC, and (iii) to investigate the stability of seven MC analogs (4-MMC, 4-, 3-, or 2-fluoromethcathinone, 4-methoxymethcathinone, N-ethylcathinone, and N,N-dimethylcathinone) in solutions at different pHs.1-(4-Methylphenyl)-1,2-propanedione (MPPD), 4-methylbenzoic acid (MBA), N,4-dimethylbenzamide (DMBA), and N-acetyl-4-MMC (N-Ac-4-MMC) were identified as the degradation products of 4-MMC in pH 12 solution by gas chromatography-mass spectrometry. There are two degradation pathways for 4-MMC as follows: (a) 4-MMC→MPPD→MBA→DMBA and (b) 4-MMC→N-Ac-4-MMC. Oxidants such as dissolved oxygen were presumed to be involved in this degradation based on the suppressive effects generated by the addition of antioxidants. All of the seven MC analogs tested were stable in acidic (pH 4) solution but degraded in neutral-to-basic solutions. Their degradation rates increased with increasing pH, and varied with their chemical structures. These findings will be very useful for not only forensic analysis but also future pharmacokinetic analysis.  相似文献   

6.
11-Nor-Delta(9)-carboxy tetrahydrocannabinol glucuronide (THCCOOglu) is a major metabolite of tetrahydrocannabinol in blood. Despite its mass spectrometric identification already in 1980, further physicochemical data of THCCOOglu have not been established. Therefore, the octanol/buffer partition coefficient P and the blood to plasma ratio b/p for THCCOOglu concentrations of 100 and 500ng/ml were investigated. Protein binding of the glucuronide was established from spiked albumin solutions at a level of 250ng/ml as well as from authentic samples. The data were compared to those of 11-nor-Delta(9)-carboxy tetrahydrocannabinol (THCCOOH). In addition, the short-term stability of THCCOOglu in plasma at different storage temperatures was studied. Analysis was performed by LC/MS/MS. The glucuronide partition coefficient P (mean: 17.4 and 18.0 for 100 and 500ng/ml, respectively) was unexpectedly lipophilic at pH 7.4. Its blood to plasma ratios averaged 0.62 and 0.68 at 100 and 500ng/ml, respectively. THCCOOglu was highly reversibly bound to albumin (mean: 97%), and the mean fraction bound did not differ from that determined from authentic samples. THCCOOglu degraded even at a storage temperature of 4 degrees C and THCCOOH was identified as a major decomposition product.  相似文献   

7.
The requirement to differentiate between incorporation and external contamination of drugs into hair is undisputed, in particular when dealing with compounds which are administered by sniffing or inhalation (e.g. cocaine). With the aim of making this discrimination, hair samples from cocaine (COC) users (group IN) and seized cocaine samples (group OUT) were compared regarding the parameters benzoylecgonine (BZE), ecgonine methyl ester (EME), ecgonine (ECG), anhydroecgonine methyl ester (AEME), cocaethylene (CE) and norcocaine (NCOC). Since most of these compounds may be minor by-products of COC or be formed by biotransformation or chemical degradation, the stability of each substance was carefully examined. COC was found to be converted into significant amounts of BZE, EME and ECG even under mild extraction conditions, while traces of NCOC proved to be a ubiquitous by-product of COC. Cocaine positive hairs and seized cocaine samples (diluted to relevant concentrations) were equally preprocessed and analyzed by LC-MS-MS. Out of the metabolites listed above, NCOC, CE and AEME (each normalised to COC) were significantly increased in the incorporation group (i.e. hair samples from cocaine users). Based on this approach, a statistical discriminant analysis enabled us to make a prediction (and estimation of uncertainty) for each cocaine positive hair sample as to its likelihood of belonging to the group of cocaine users or of being contaminated.  相似文献   

8.
Lawsone is a 2‐substituted‐1,4‐naphthoquinone derivative, which has been proposed as an alternative to the reagents currently used for fingermark detection on porous surfaces. 2‐substituted‐anthraquinones, which contain an additional conjugated benzene ring, have a similar chemical structure to that of lawsone. In this study, a new series of 2‐substituted‐1,4‐naphthoquinones and 2‐substituted‐1,4‐anthraquinones were synthesized and completely characterized by1H NMR,13C NMR, IR, and HPLC‐TOF/MS analyses. All newly synthesized 2‐substituted‐1,4‐quinones were investigated for their ability to develop latent fingermarks on porous surfaces, and this ability was compared with that of lawsone. Each fingermark developed was graded using an established method; thus, quantitative data were attributed to each fingermark. It has been demonstrated that the 1,4 ‐ quinones react with amino acids present in latent fingermarks on selected paper surfaces to produce faint yellow‐orange impressions, which exhibit strong photoluminescence when illuminated with a forensic light source at 440 nm and observed through a red filter. None of the compounds caused background darkening. The results obtained were generally similar to those of lawsone, however, 8‐dibromo‐2‐(propylamino)naphthalene‐1,4‐dione and 5,8‐dibromo‐2‐(propylthio)naphthalene‐1,4‐dione yielded better results for copier paper and colored (blue) copier paper used in this analysis. To the best of our knowledge, this is the first study to examine the role of 1,4‐anthraquinone derivatives as potential fingermark development reagents. The results indicate that 1,4‐quinones have a potential to be used as reagents for enhancement of latent fingermarks.  相似文献   

9.
Diazepam is one of the mostly used benzodiazepines and it is frequently analyzed in different biological samples, especially blood samples. The diazepam stability in the sample matrices is an important factor regarding reliable data obtaining. The storage is the main factor determining the stability of diazepam in blood samples and it is the object of the study presented. Remaining diazepam amount in spiked whole blood and plasma samples were tested at different storage temperatures, in the absence or presence of sodium fluoride as stabilizer as well as the influence of ethanol on diazepam stability was evaluated. The results of the study indicated that the temperature is the main storage factor affecting diazepam stability. In the fluoride stabilized blood samples the amount of diazepam decreases up to 85% of initial level when stored at -20° C for the period of testing (12 weeks). The presence of low (0.5 g/L) or high (3g/L) ethanol concentrations influences the stability of diazepam at -20 °C. In whole blood samples, the combination of sodium fluoride and ethanol decreases additionally (15-25%) the concentration of the analyte. Freeze-thaw experiments of whole blood samples show about 5-9% decrease in diazepam concentration after the first cycle. The freeze-thaw experiments on plasma samples, containing ethanol and/or fluoride show insignificant decreases of analyte concentration. Further experiments on benzodiazepines stability at different storage conditions or in combination of different factors should be undertaken in forensic toxicology to ensure the data quality, their reliability and reproducibility.  相似文献   

10.
目的采用SPE-LC-MS/MS方法,同时检测尿液与血液中海洛因主要代谢物3-β-D-葡萄糖醛酸吗啡(M3G)、吗啡和O6-单乙酰吗啡(O6)。方法采用BAKERBONDTMspe Octadecyl(C18)进行提取,应用LC-MS/MS方法检测并通过MRM及内标法进行量化。结果尿液中M3G、吗啡、O6-单乙酰吗啡的最低检测限(LOD)分别为1.24pg、6.71pg、0.47pg;回收率依次为82.25±12.25%、93.75±13.25%、88.70±11.90%。血液中M3G、吗啡、O6-单乙酰吗啡的最低检测限分别为1.50pg、8.21pg、0.52pg。回收率依次为89.85±21.15%、73.70±17.90%、90.10±3.90%。结论本文所建方法同时适用于尿液与血液中海洛因主要代谢物M3G、吗啡、O6-单乙酰吗啡的提取、净化、分析。  相似文献   

11.
Currently, no established methodology exists to determine degradation patterns of latent fingermarks by visual means. This article is the second in a series of reports exploring quantifiable degradation‐related parameters, which focuses on color contrast changes between fingermark ridges and furrows over time. Experiment variables included type of secretion (eccrine and sebaceous), substrate (glass and plastic), and exposure to natural light (dark, shade, and direct light). Fingermarks were sequentially visualized with titanium dioxide powder and photographed. Image histogram profiles were evaluated and combined with statistical analysis of color data values. Results indicate that sebaceous depositions on glass were generally less degraded by the effect of environmental conditions compared with those on plastic. In addition, aging in darkness was not always the best condition for preservation, and direct exposure to light seemed to inhibit visual degradation under certain conditions. Overall, the technique provided sufficient sensitivity to discern degradation patterns of fingermarks.  相似文献   

12.
The results of extraction of 1,2- and 1,4-dihydroxybenzene from water solutions by the hydrophobic and hydrophilic organic solvents are described. The influence of an extragent nature and of a water-phase pH medium on an extraction degree is demonstrated. The repetition factor needed to extract a preset quantity of examined compounds is calculated.  相似文献   

13.
Oral fluid (collected with the Intercept((R)) device) and plasma samples were obtained from 139 individuals suspected of driving under the influence of drugs and analyzed for Delta(9)-tetrahydrocannabinol (THC), the major psychoactive constituent of cannabis, using a validated quantitative LC-MS-MS method. The first aim of the study was to investigate the correlation between the analytical data obtained in the plasma and oral fluid samples, to evaluate the use of oral fluid as a 'predictor' of actual cannabis influence. The results of the study indicated a good accuracy when comparing THC detection in oral fluid and plasma (84.9-95.7% depending on the cut-off used for plasma analysis). ROC curve analysis was subsequently used to determine the optimal cut-off value for THC in oral fluid with plasma as reference sample, in order to 'predict' a positive plasma result for THC. When using the LOQ of the method for plasma (0.5 ng/mL), the optimal cut-off was 1.2 ng/mL THC in oral fluid (sensitivity, 94.7%; specificity, 92.0%). When using the legal cut-off in Belgium for driving under the influence in plasma (2 ng/mL), an optimal cut-off value of 5.2 ng/mL THC in oral fluid (sensitivity, 91.6%; specificity, 88.6%) was observed. In the second part of the study, the performance of the on-site Dr?ger DrugTest for the screening of THC in oral fluid during roadside controls was assessed by comparison with the corresponding LC-MS-MS results in plasma and oral fluid. Since the accuracy was always less than 66%, we do not recommend this Dr?ger DrugTest system for the on-site screening of THC in oral fluid.  相似文献   

14.
The present study was designed to determine the stability of pancuronium in postmortem blood and liver during storage. Results were obtained using the method by Kerskes et al. [C.H.M. Kerskes, K.J. Lusthof, P.G.M. Zweipfenning, J.P. Franke, The detection and identification of quaternary nitrogen muscle relaxants in biological fluids and tissues by ion-trap LC-ESI-MS, J. Anal. Toxicol. 26 (2002) 29-34.], modified and validated in our laboratory. Target analytes were isolated after enzymatic hydrolysis followed by solid phase extraction (BondElut C18 column). Internal standardisation was carried out using laudanosine and the target ions were monitored by LC-ESI-MS (monitoring ions m/z 358 for IS and 286 for pancuronium). Materials were taken from a 46-year-old woman, who had been found dead. A syringe (2 ml) and an empty ampoule of Pavulon (4 mg/2 mL) were found in her hand. The residual volume of fluid in the syringe was 0.7 ml. An autopsy was performed six days after death. It revealed a needle mark on the left thigh. Postmortem materials (muscle from the injection site, blood and liver) and the syringe with fluid were stored for four months in a freezer at -20 degrees C. The initial pancuronium concentrations were 81 ng/mL in blood and 532 ng/g in liver. The analyte was stable when stored at -20 degrees C in blood even up to seven months. In liver samples its concentrations were variable. Pancuronium in blood stored at 20 degrees C underwent degradation very rapidly. After three months of storage these blood samples had concentrations not greater about 10% of the initial value. The degradation patterns of pancuronium depended on temperature and the biological matrix.  相似文献   

15.
The detection of a mixture of nine explosive compounds, including nitrate esters, nitroaromatics, and a nitramine in less than 140 sec is described. The new method employs a commercially available pulsed-discharge electron capture detector (PDECD) coupled with a microbore capillary gas chromatography (GC) column in a standard GC oven to achieve on-column detection limits between 5 and 72 fg for the nine explosives studied. The PDECD has the benefit that it uses a pulsed plasma to generate the standing electron current instead of a radioactive source. The fast separation time limits on-column degradation of the thermally labile compounds and decreases the peak widths, which results in larger peak intensities and a concomitant improvement in detection limits. The combination of short analysis time and low detection limits make this method a potential candidate for screening large numbers of samples that have been prepared using techniques such as liquid-liquid extraction or solid-phase microextraction.  相似文献   

16.
The in vitro stability of cocaine in horse blood, sheep vitreous humour (VH) and homogenised deer muscle is described. The stability of cocaine in horse blood was of interest because many toxicology laboratories utilise horse blood for the preparation of calibration and check standards and the latter are typically stored during routine use. The storage stability of cocaine in human VH and muscle has not been previously reported. In the absence of blank human VH and muscle, cocaine stability under varying conditions was demonstrated in animal tissues. Blood and VH were stored with and without addition of NaF at room temperature (RT), 4°C and -18°C for 84 days. Muscle homogenates were prepared in water, water/2% NaF, and phosphate buffer (pH 6.0)/2% NaF, and stored for 31 days at RT, 4°C and -18°C. Cocaine stability in human muscle obtained from cocaine positive forensic cases was assessed following storage at -18°C for 13 months. Cocaine and benzoylecgonine (BZE) were extracted using SPE and quantified by GC-MS/MS. Cocaine was stable for 7 days in refrigerated (4°C) horse blood fortified with 1 and 2% NaF. In the absence of NaF, cocaine was not detectable by day 7 in blood stored at RT and 4°C and had declined by 81% following storage at -18°C. At 4°C the rate of cocaine degradation in blood preserved with 2% NaF was significantly slower than with 1% NaF. The stability of cocaine in horse blood appeared to be less than that reported for human blood, probably attributable to the presence of carboxylesterase in horse plasma. Cocaine stored in VH at -18°C was essentially stable for the study period whereas at 4°C concentrations decreased by >50% in preserved and unpreserved VH stored for longer than 14 days. Fluoride did not significantly affect cocaine stability in VH. The stability of cocaine in muscle tissue homogenates significantly exceeded that in blood and VH at every temperature. In preserved and unpreserved samples stored at 4°C and below, cocaine loss did not exceed 2%. The increased stability of cocaine in muscle was attributed to the low initial pH of post-mortem muscle. In tissue from one human case stored for 13 months at -18°C the muscle cocaine concentration declined by only 15% (range: 5-22%). These findings promote the use of human muscle as a toxicological specimen in which cocaine may be detected for longer compared with blood or VH.  相似文献   

17.
Evaluation of cannabinoid concentrations in products from the legal cannabis market has been fraught with uncertainty. The lack of standardized testing methodology and the susceptibility of cannabinoids to degradation under certain storage conditions complicates the efforts to assess total tetrahydrocannabinol (THC) levels across wide geographic areas. There are few peer-reviewed surveys of cannabinoid concentrations in regulated products. Those that have been done have not characterized the effects of differences in analytical methodology, sample population, and storage conditions. Viridis Laboratories, which operates two cannabis safety compliance facilities in Michigan, has analyzed over 34,000 cannabis products throughout 2021 and 2022 before the sale in the regulated market. Fifteen cannabinoids in cannabis flower, concentrates, and infused products were tested using methanolic extraction and analysis by high-performance liquid chromatography with diode-array detection. Methods were validated before use, and the flower analysis procedure was certified by the Association of Analytical Collaboration. All the samples were tested before submission for sale and therefore had not undergone prolonged storage. The results are compared with those seen in other states as well as in the illicit market. Total THC levels in cannabis flower from the regulated market are significantly higher than those seen in illicit products. The distribution of cannabinoid levels is similar in flowers intended for either the medicinal or adult-use markets, with an average potency of 18%–23% of total THC. Total THC in concentrates averages up to 82%. Other cannabinoids are observed at significant levels, mostly in products specifically formulated to contain them. These results may act as a benchmark for potency levels in the regulated market.  相似文献   

18.
Ignitable liquid residues recovered from a fire scene will often show signs of weathering as a result of exposure to the heat of the fire. In addition, when the substrate is rich in organic matter, both weathering and microbial degradation may be observed. In this study, 20 μL aliquots of fresh gasoline samples were intentionally weathered and also subjected to microbial degradation in potting soil. These samples were then analyzed using a passive adsorption-elution recovery method and gas chromatography/mass spectrometry. Peak areas from compounds of interest were normalized and autoscaled and then subjected to principal components analysis. This analysis showed that while lower boiling compounds are subject to weathering, a different set of compounds are subject to microbial degradation. Of the compounds studied, heptane, octane, toluene, and ethylbenzene were the most vulnerable to both weathering and microbial degradation. In contrast, 1,3,5-trimethylbenzene and 2-ethyltoluene were the most resistant to both phenomena.  相似文献   

19.
The storage and use of explosives is regulated at the state and federal level, with a particular focus on physical security and rigorous accounting of the explosive inventory. For those working with explosives for the training and testing of explosive-detecting canines, cross-contamination is an important concern. Hence, explosives intended for use with canine teams must be placed into secondary storage containers that are new, clean, and airtight. A variety of containers meet these requirements and include screw-top glass jars (e.g., mason jars). However, an additional need from the explosive-detecting canine community is secondary containers that can also be used as training aids whereby the volatiles emitted by explosives are emitted in a predictable and stable manner. Currently, a generally accepted method for the storage of explosives and controlled emission of explosive vapor for canine detection does not exist. Ideally, such containers should allow odor to escape from the training aid but block external contaminates such as particulates or other volatiles. One method in use places the explosive inside a permeable cotton bag when in use for training and then stores the cotton bag inside an impermeable nylon bag for long-term storage. This paper describes the testing of an odor permeable membrane device (OPMD) as a new way to store and deploy training aids. We measured the evaporation rate and flux of various liquid explosives and volatile compounds that have been identified in the headspace of actual explosives. OPMDs were used in addition to traditional storage containers to monitor the contamination and degradation of 14 explosives used as canine training aids. Explosives were stored individually using traditional storage bags or inside an OPMD at two locations, one of which actively used the training aids. Samples from each storage type at both locations were collected at 0, 3, 6, and 9 months and analyzed using Fourier Transform Infrared (FTIR) Spectroscopy and Gas Chromatography–Mass Spectrometry (GC–MS) with Solid-Phase Microextraction (SPME). FTIR analyses showed no signs of degradation. GC–MS identified cross-contamination from ethylene glycol dinitrate (EGDN) and/or 2,3-dimethyl-2,3-dinitrobutane (DMNB) across almost all samples regardless of storage condition. The contamination was found to be higher among training aids that were stored in traditional ways and that were in active use by canine teams.  相似文献   

20.
The preanalytic phase has been recognized to have a substantial role for the quality and reliability of analytical results, which very much depend on the type and quality of specimens provided. There are several unique challenges to select and collect specimens for postmortem toxicology investigation. Postmortem specimens may be numerous, and sample quality may be quite variable. An overview is given on specimens routinely collected as well as on alternative specimens that may provide additional information on the route of administration, a long term or a recent use/exposure to a drug or poison. Autolytic and putrefactive changes limit the selection and utility of specimens. Some data from case reports as well as experimental investigations on drug degradation and/or formation during putrefaction are discussed. Diffusion processes as well as postmortem degradation or formation may influence ethanol concentration in autopsy specimens. Formalin fixation of specimens or embalmment of the corpse may cause considerable changes of initial drug levels. These changes are due to alterations of the biological matrix as well as to dilution of a sample, release or degradation of the drug or poison. Most important seems a conversion of desmethyl metabolites to the parent drug. Some general requirements for postmortem sampling are given based on references about specimen collection issues, for a harmonized protocol for sampling in suspected poisonings or drug-related deaths does not exist. The advantages and disadvantages of specimen preservation are shortly discussed. Storage stability is another important issue to be considered. Instability can either derive from physical, chemical or metabolic processes. The knowledge on degradation mechanisms may enable the forensic toxicologist to target the right substance, which may be a major break down product in the investigation of highly labile compounds. Although it is impossible to eliminate all interfering factors or influences occurring during the preanalytic phase, their consideration should facilitate the assessment of sample quality and the analytical result obtained from that sample.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号