Cocaine and crack cocaine are usually seized with a great diversity of adulterants, such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these drug mixtures is normally perf...Cocaine and crack cocaine are usually seized with a great diversity of adulterants, such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences providing false-positive or false-negatives. In this work, we describe the use of thin layer chromatography coupled to easy sonic-spray ambient ionization mass spectrometry (TLC/EASI-MS) for rapid and secure analysis of cocaine and crack cocaine. Fifteen cocaine samples were analyzed, and all of them revealed positive TLC/EASI-MS results for cocaine, but other drugs and adulterants were also detected such as lidocaine, caffeine, benzocaine, lactose, benzoylecgonine, and ecgonidine. False positives and false negatives, as judged by the TLC Rf values, were identified via on-spot characterization by EASI-MS. The TLC/EASI-MS combination seems therefore to provide an appropriate technique for secure forensic investigations of illicit drugs.展开更多
Fast and unequivocal methods of questioned document analysis are essential in forensic science. Here, a desorption/ionization technique, EASI-MS, was assessed for its ability to investigate questioned driver’s licens...Fast and unequivocal methods of questioned document analysis are essential in forensic science. Here, a desorption/ionization technique, EASI-MS, was assessed for its ability to investigate questioned driver’s licenses (DL). Two suspects DL, displaying the same personal data in the proper fields (name and ID numbers), but with different individual photos, showing similar impressions on microscopic analysis, and authentic standards documents specimens were used as test cases. Profiles from authentic DL surface were dominated by a set of few minor ions, mainly from the plasticizers bis(2-ethylhexyl)phthalate and dibutylphthalate. The seized suspect counterfeit DL on points from personal data and photo were, however, dominated by abundant diagnostic ions of m/z 463, 507, 551, 595, 639, 683, which confirmed counterfeiting. Surfynol<sup>®</sup> and Nonoxynol-9<sup>®</sup>, which are common constituents of inkjet printing, were detected in the counterfeiting areas by high-accuracy EASI(+)-FT-ICR MS. The EASI-MS technique is shown therefore to offer an attractive tool for forensic investigation of questioned documents.展开更多
Direct infusion electrospray ionization mass spectrometry (ESI-MS) is shown to provide an efficient tech- nique for the investigation of polar composition of forensic tablets for male erectile dysfunction. ESI-MS fing...Direct infusion electrospray ionization mass spectrometry (ESI-MS) is shown to provide an efficient tech- nique for the investigation of polar composition of forensic tablets for male erectile dysfunction. ESI-MS fingerprinting of 41 commercial sildenafil samples (Viagra?, Cialis?, Lazar?, Libiden?, , Maxfil?, , Plenovit?, Potent 75?, Rigix?, V-50?, Vimax?, Pramil 75? and Pramil?) and 56 counterfeit samples (Viagra and Cialis) were obtained. The spectra for the authentic Viagra? tablets showed abundant ions exclusively corresponding to the sildenafil (SLD) molecule: [SLD + H]+ of m/z 475;[SLD + Na]+ of m/z 497;and [2SLD + H]+ of m/z 949. The spectra for com-mercial sildenafil samples also showed predominat SLD ions. Tablets of authentic Cialis? showed mainly ions of m/z 343, 365 and 707 from the lactose molecule (the excipient);as well as a minor ion of m/z 390 corresponding to the active ingredient tadalafil (TAD) in its protonated form [TAD + H]+. For counterfeit Cialis samples, how-ever, normally TAD ions of much high abundances was observed, together with ions corresponding to sildenafil analogues such as those of m/z 489 (homosildenafil) and 505 (hydroxyhomosildenafil). Principal component analysis was applied to ESI-MS fingerprint data, placing samples according to their contents of active ingredients hence authentic and counterfeit samples are easily recognized.展开更多
The increasing demand for safe food without preservatives or pesticides residues has encouraged several studies on natural products with antifungal activity and low toxicity.In this study,ethanolic extracts from leave...The increasing demand for safe food without preservatives or pesticides residues has encouraged several studies on natural products with antifungal activity and low toxicity.In this study,ethanolic extracts from leaves and fruit residues(peel and seeds)of three Brazilian savanna species(Acrocomia aculeata,Campomanesia adamantium and Caryocar brasiliense)were evaluated against phytopathogenic fungi.Additionally,the most active extract was chemically characterized by ESI-MS and its oral acute toxicity was evaluated.Extracts from C.brasiliense(pequi)peel and leaves were active against Alternaria alternata,Alternaria solani and Venturia pirina with minimal inhibitory concentrations between 350 and 1000 lg/mL.When incorporated in solid media,these extracts extended the lag phase of A.alternata and A.solani and reduced the growth rate of A.solani.Pequi peel extract showed better antifungal activity and their ESI-MS analysis revealed the presence of substances widely reported as antifungal such as gallic acid,quinic acid,ellagic acid,glucogalin and corilagin.The oral acute toxicity was relatively low,being considered safe for use as a potential natural fungicide.展开更多
The antioxidant capacity and changes in chemical composition of two grape varieties, the new hybrid BRS-Carmem and the Bord6 grape （Vitis labrusca） and of their products （juice, wine and vinegar） were evaluated by...The antioxidant capacity and changes in chemical composition of two grape varieties, the new hybrid BRS-Carmem and the Bord6 grape （Vitis labrusca） and of their products （juice, wine and vinegar） were evaluated by several techniques. The DPPH method was used to measure the antioxidant capacity, whereas, the total phenolic contents （TPC） were measured by Folin-Ciocalteau method. Overall chemical composition was also monitored by ESI-MS fingerprints and UPLC-MS analysis. For both grape varieties, the highest （and similar） antioxidant capacity and TPC were observed for the wine and vinegar samples followed by the grapes and then the juices. In addition, ESI-MS fingerprints and UPLC-MS analysis in the negative ion mode indicated substantial changes in chemical composition from grape to juice and wine, and then to vinegar.展开更多
基金financial support from the Brazilian Science foundations CNPq,FAPESP,FINEP and Inmetro.
文摘Cocaine and crack cocaine are usually seized with a great diversity of adulterants, such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences providing false-positive or false-negatives. In this work, we describe the use of thin layer chromatography coupled to easy sonic-spray ambient ionization mass spectrometry (TLC/EASI-MS) for rapid and secure analysis of cocaine and crack cocaine. Fifteen cocaine samples were analyzed, and all of them revealed positive TLC/EASI-MS results for cocaine, but other drugs and adulterants were also detected such as lidocaine, caffeine, benzocaine, lactose, benzoylecgonine, and ecgonidine. False positives and false negatives, as judged by the TLC Rf values, were identified via on-spot characterization by EASI-MS. The TLC/EASI-MS combination seems therefore to provide an appropriate technique for secure forensic investigations of illicit drugs.
文摘Fast and unequivocal methods of questioned document analysis are essential in forensic science. Here, a desorption/ionization technique, EASI-MS, was assessed for its ability to investigate questioned driver’s licenses (DL). Two suspects DL, displaying the same personal data in the proper fields (name and ID numbers), but with different individual photos, showing similar impressions on microscopic analysis, and authentic standards documents specimens were used as test cases. Profiles from authentic DL surface were dominated by a set of few minor ions, mainly from the plasticizers bis(2-ethylhexyl)phthalate and dibutylphthalate. The seized suspect counterfeit DL on points from personal data and photo were, however, dominated by abundant diagnostic ions of m/z 463, 507, 551, 595, 639, 683, which confirmed counterfeiting. Surfynol<sup>®</sup> and Nonoxynol-9<sup>®</sup>, which are common constituents of inkjet printing, were detected in the counterfeiting areas by high-accuracy EASI(+)-FT-ICR MS. The EASI-MS technique is shown therefore to offer an attractive tool for forensic investigation of questioned documents.
文摘Direct infusion electrospray ionization mass spectrometry (ESI-MS) is shown to provide an efficient tech- nique for the investigation of polar composition of forensic tablets for male erectile dysfunction. ESI-MS fingerprinting of 41 commercial sildenafil samples (Viagra?, Cialis?, Lazar?, Libiden?, , Maxfil?, , Plenovit?, Potent 75?, Rigix?, V-50?, Vimax?, Pramil 75? and Pramil?) and 56 counterfeit samples (Viagra and Cialis) were obtained. The spectra for the authentic Viagra? tablets showed abundant ions exclusively corresponding to the sildenafil (SLD) molecule: [SLD + H]+ of m/z 475;[SLD + Na]+ of m/z 497;and [2SLD + H]+ of m/z 949. The spectra for com-mercial sildenafil samples also showed predominat SLD ions. Tablets of authentic Cialis? showed mainly ions of m/z 343, 365 and 707 from the lactose molecule (the excipient);as well as a minor ion of m/z 390 corresponding to the active ingredient tadalafil (TAD) in its protonated form [TAD + H]+. For counterfeit Cialis samples, how-ever, normally TAD ions of much high abundances was observed, together with ions corresponding to sildenafil analogues such as those of m/z 489 (homosildenafil) and 505 (hydroxyhomosildenafil). Principal component analysis was applied to ESI-MS fingerprint data, placing samples according to their contents of active ingredients hence authentic and counterfeit samples are easily recognized.
基金We are grateful to SaōPaulo Research Foundation for the financial support of this research and for the fellowships awarded to C.A.B.(FAPESP No.2011/19057-7)G.A.B.(FAPESP No.2012/21395-0)to Study Group of Cerrado Agroindustrial Processes(GEPPAC)of the Federal University of Grande Dourados to provide laboratories for plant material processing step.
文摘The increasing demand for safe food without preservatives or pesticides residues has encouraged several studies on natural products with antifungal activity and low toxicity.In this study,ethanolic extracts from leaves and fruit residues(peel and seeds)of three Brazilian savanna species(Acrocomia aculeata,Campomanesia adamantium and Caryocar brasiliense)were evaluated against phytopathogenic fungi.Additionally,the most active extract was chemically characterized by ESI-MS and its oral acute toxicity was evaluated.Extracts from C.brasiliense(pequi)peel and leaves were active against Alternaria alternata,Alternaria solani and Venturia pirina with minimal inhibitory concentrations between 350 and 1000 lg/mL.When incorporated in solid media,these extracts extended the lag phase of A.alternata and A.solani and reduced the growth rate of A.solani.Pequi peel extract showed better antifungal activity and their ESI-MS analysis revealed the presence of substances widely reported as antifungal such as gallic acid,quinic acid,ellagic acid,glucogalin and corilagin.The oral acute toxicity was relatively low,being considered safe for use as a potential natural fungicide.
文摘The antioxidant capacity and changes in chemical composition of two grape varieties, the new hybrid BRS-Carmem and the Bord6 grape （Vitis labrusca） and of their products （juice, wine and vinegar） were evaluated by several techniques. The DPPH method was used to measure the antioxidant capacity, whereas, the total phenolic contents （TPC） were measured by Folin-Ciocalteau method. Overall chemical composition was also monitored by ESI-MS fingerprints and UPLC-MS analysis. For both grape varieties, the highest （and similar） antioxidant capacity and TPC were observed for the wine and vinegar samples followed by the grapes and then the juices. In addition, ESI-MS fingerprints and UPLC-MS analysis in the negative ion mode indicated substantial changes in chemical composition from grape to juice and wine, and then to vinegar.
