Chemical profiling of the street cocktail drug ‘nyaope’ in South Africa using gas chromatography-mass spectrometry (GC-MS)

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Date
2020
Authors
Mthembi, Pabalala Meshack
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University of the Free State
Abstract in other languages 𝘚𝘤𝘳𝘰𝘭𝘭 𝘥𝘰𝘸𝘯 𝘧𝘰𝘳 𝘈𝘧𝘳𝘪𝘬𝘢𝘢𝘯𝘴, 𝘚𝘦𝘚𝘰𝘵𝘩𝘰 𝘢𝘯𝘥 𝘐𝘴𝘪𝘡𝘶𝘭𝘶
Abstract
𝑬𝒏𝒈𝒍𝒊𝒔𝒉 The street cocktail drug nyaope, commonly found in South Africa, is a mixture of low-grade heroin, cannabis products, antiretroviral drugs and other materials added as bulking agents. This research led to the development of an analytical method for the identification and profiling of the street cocktail drug nyaope, using gas chromatography – mass spectrometry. This study determined for the first time the most suitable organic solvent in which the common components of nyaope, namely Δ9-tetrahydrocannabinol, heroin, caffeine, dextromethorphan, phenacetin and the antiretrovirals efavirenz and nevirapine, which have different chemical characteristics, are stable prior to an analysis of nyaope samples. The main nyaope components, when extracted into tertiary butyl alcohol, exhibited the greatest autosampler stability of up to 72 hours of storage. From these results it can be determined that tertiary butyl alcohol is a suitable solvent for the identification, comparison and profiling of nyaope samples. With regard to analytical method validation, the method gave acceptable repeatability with the %RSD less than 10% for the 10.0 and 1000.0 mg/L concentration levels for the majority of the components. The linear concentration ranges managed linearity with r2 ≥ 0.997. The detection limits varied between 9.90–39.0 pg on column and the limit of quantitation between 30.0–120 pg on column. The method exhibited acceptable recoveries and ruggedness. The method developed is fit for the purpose of quantitative profiling of the major components of nyaope using gas chromatography-mass spectrometry. The majority of the components in the street cocktail drug nyaope were shown to be stable up to at least 24 hours when stored in a refrigerator. For profiling purposes, samples need to be extracted within 24 hours of seizure in a solvent in which they are stable, such as tertiary butyl alcohol and analysed within 72 hours. At all times the samples need to be protected from light to prevent the photo-decomposition of Δ9-tetrahydrocannabinol and from moisture to prevent the hydrolysis of diamorphine. The chemical components of simulated nyaope samples as well as actual seized street nyaope samples were successfully identified and quantitatively determined using gas chromatography – mass spectrometry. The simulated and actual seized street samples were successfully discriminated into original batches using the identified nyaope components and two unsupervised chemometric methods, namely principal component analysis and hierarchical clustering, as well as chromatographic profiles. Thus, for the first time, a validated analytical method has been developed for the identification, quantitation and profiling of nyaope using gas chromatography – mass spectrometry. The method will assist law enforcement agencies in the identification and comparison of nyaope samples and facilitate the prosecution of illicit drug trafficking offences. ___________________________________________________________________
𝑨𝒇𝒓𝒊𝒌𝒂𝒂𝒏𝒔 Die straatdwelmmengsel “nyaope”, wat algemeen in Suid-Afrika aangetref word, is 'n mengsel van laegraadse heroïen, daggaprodukte, antiretrovirale middels en ander materiaal wat bygevoeg word. Hierdie navorsing het gelei tot die ontwikkeling van 'n analitiese metode om die straatdwelm nyaope met behulp van gaschromatografie en massaspektrometrie te identifiseer en ’n profiel daar te stel. Hierdie studie het vir die eerste keer die mees geskikte organiese oplosmiddel bepaal waarin die algemene komponente van nyaope, naamlik Δ9-tetrahydrocannabinol, heroïen, kafeïen, dekstrometorfan, fenasetien en die antiretrovirale middels efavirens en nevirapien, wat verskillende chemiese eienskappe het, stabiel is voor die ontleding van nyaope-monsters. Die belangrikste nyaope-komponente, wanneer dit in tersiêre butielalkohol onttrek is, het die grootste outo-monsterstabiliteit van tot 72 uur se berging getoon. Uit hierdie resultate kan bepaal word dat tersiêre butielalkohol 'n geskikte oplosmiddel is vir die identifikasie, vergelyking en profilering van nyaope monsters. Met betrekking tot die validering van ’n analitiese metode, het die metode aanvaarbare herhaalbaarheid gegee met die %RSD minder as 10% vir die 10.0 en 1000.0 mg/L konsentrasievlakke vir die meerderheid van die komponente. Die lineêre konsentrasiereekse bestuur lineariteit met r2 ≥ 0,997. Die opsporingslimiete het gewissel tussen 9.90–39.0 (pg on column) en die limiet van kwantifisering tussen 30.0–120 (pg on column). Die metode het aanvaarbare herstel en robuustheid getoon. Die metode wat ontwikkel is, is geskik vir die doel van kwantitatiewe profilering van die hoofkomponente van nyaope deur gebruik te maak van gaschromatografie-massaspektrometrie. Die meerderheid van die komponente in die straatdwelmmengsel nyaope het getoon dat dit stabiel is vir tot ten minste 24 uur wanneer dit in 'n yskas gestoor word. Vir profieldoeleindes moet monsters binne 24 uur ná beslaglegging onttrek word en binne 72 uur in ’n oplosmiddel ontleed word waarin hulle stabiel is, soos tersiêre butielalkohol. Die monsters moet te alle tye teen lig beskerm word, om die foto-ontbinding van Δ9-tetrahidrokannabinol te voorkom, asook teen vog, om die hidrolise van diamorfien te voorkom. Die chemiese komponente van gesimuleerde nyaope-monsters sowel as werklike, gekonfiskeerde straatmonsters is suksesvol geïdentifiseer en kwantitatief bepaal met behulp van gaschromatografie – massaspektrometrie. Die gesimuleerde en werklike, gekonfiskeerde straatmonsters is suksesvol verdeel in oorspronklike groepe deur gebruik te maak van die geïdentifiseerde nyaope-komponente en twee ongeverifieerde chemometriese metodes, naamlik hoofkomponent-analise en hiërargiese groepering, sowel as chromatografiese profiele. So, vir die eerste keer is 'n bekragtigde analitiese metode ontwikkel vir die identifikasie, kwantifisering en profilering van nyaope met behulp van gaschromatografie – massaspektrometrie. Die metode sal wetstoepassingsagentskappe help met die identifisering en vergelyking van nyaope-monsters en die vervolging van onwettige dwelmhandelmisdrywe vergemaklik. ___________________________________________________________________
𝑺𝒆𝑺𝒐𝒕𝒉𝒐 Sethethefatsi sa meketeng sa ‘nyaope’ seo hangata se fumanwang mona Afrika Borwa, ke motswako wa herion ya boemo bo tlase, dihlahiswa tsa matekwane (cannabis), dithethefatsi tsa antiretrovaerale le thepa e nngwe e ekeditsweng ka dipokello tse ngata. Diphuputso tsena di ile tsa baka hore ho be le mokgwa ona wa tshekatsheko bakeng sa ho hlwaya le ho bontsha dikateng tsa sethethefatsi sena sa meketeng ya seterata sa ‘nyaope’, ka ho sebedisa gas chromatography – mass spectrometry. Diphuputso tsena di ikemiseditse ka lekgetlo la pele ho sebedisa seqhibidihi se loketseng e leng moo ho nang le dikarolo tse tlwaelehileng tsa ‘nyaope’, e leng Δ9 -tetrahydrocannabinol, heroin, caffeine, dextromethorphan, phenacetin esita le antiretrovirals efavirenz hammoho le nevirapine, tse nang le dikarolwana tse fapaneng tsa dikhemikhale, di tsitsitse pele ho tshekatsheko ya disampole tsa ‘nyaope’. Dikarolo tse kgolo tsa ‘nyaope’ ha di ntshetswa ho motswako wa tahi wa tertiary butyl alcohol, di bontshitse botsitso bo boholo ba disampole ka botsona ho fihla nakong ya ho bolokwa ka dihora tse 72. Ho tswa diphethong tsena, ho ka hlokomelwa hore tertiary butyl alcohol ke motswako o tshwanelehang o qhibidihang bakeng sa ho hlwaya, ho bapisa esita le ho totobatsa metswako ya disampole tsa ‘nyaope’. Bakeng sa ho nnetefatsa mokgwa wa tshekatsheko, mokgwa ona o fane ka phetapheto e amohelehang ya sephetho ka hore %RSD ka tlase ho maemo a motswako wa 10% bakeng sa 10.0 le 1000.0 mg/L bakeng sa bongata ba dikarolo. Toboketso ya motswako ka ho otloloha e kgonne ho baballa kotloloho ka r2 ≥ 0.997. Meedi ya tekolo e fapane pakeng tsa 9.90–39.0 pg ho kholomo le moedi wa teko ya bongata pakeng tsa 30.0–120 pg ho kholomo. Mokgwa ona o bontshitse diphumano le hona ho matlafala le ho tiya. Mokgwa ona o fumanweng o entsweng o loketse sepheo sa ho fumana palo ya bongata ba dikarolo tsa motheo tsa ‘nyaope’ ka ho sebedisa sesebediswa sa gas chromatography-mass spectrometry. Bongata ba dikarolo tsa sethethefatsi sena sa ‘nyaope’ sa meketeng ya seterata se bontshitswe se tsitsitse ho a fihla bonyane ho dihora tse 24 ha se bolokwa ka hara sehatsetsi. Bakeng sa ho bolokelwa nalane, disampole di lokela ho ntshwa nakong ya dihora tse 24 tsa ho hatellwa ka matla ka hara mokedikedi oo di tsitsitseng le ka ho ona, jwaloka tertiary butyl alcohol ebe di tla sekwasekwa nakong ya dihora tse 72. Ka dinako tsohle disampole di lokela ho sireletswa kganyeng e le ho thibela photo-decomposition of Δ 9 -tetrahydrocannabinol le ho mongobo e le ho thibela hydrolysis of diamorphine. Dikarolwana tsa dikhemikhale tsa disampole tse iketseditsweng tsa ‘nyaope’ esita le tsa nnete tsa mekete ya seterata tsa ‘nyaope’ di ile tsa hlwauwa ka katleho le ho tseba bongata ba tsona ka ho sebedisa gas chromatography – mass spectrometry. Disampole tsena tsa seterata tsa bonketsisane le tsa nnete di ile tsa arolwa ka katleho ka ho sebedisa dingatana le ho sebedisa dikarolo tse hlwailweng tsa ‘nyaope’ le mekgwa e mmedi e sa tataiswang ka tekolo e le mekgwa ya chemometric, e leng tshekatsheko tse kgolo tsa dikarolwana le ho di hlophisa ka dihlotshwana tsa tsona ho tloha tlase ho isa hodimo, esita le nalane ya chromatographic. Ka hona, ke ka lekgetlo la pele la ho hlwaya, ho tseba bongata ba dikarolo le ho theha nalane ya ‘nyaope’ ka ho sebedisa gas chromatography – mass spectrometry. Mokgwa ona o tla thusa basebeletsi ba tsa molao ho hlwaya le ho bapisa disampole tsa ‘nyaope’ le ho tiisa le ho potlakisa ho tshwarwa ha batlodi ba molao ba sebedisang dithethefatsi ka tsela e sa lokang. ___________________________________________________________________
𝑰𝒔𝒊𝒁𝒖𝒍𝒖 Isidakamizwa i-nyaope, evame ukutholakala eNingizimu Afrikha, iyingxube ye-heroin yezinga eliphansi, imikhiqizo yensangu, imishanguzo yokuthithibalisa igciwane lengculazi nezinye izinto ezifakwa njengama-bulking agents. Lolu cwaningo luholele ekuthuthukisweni kwendlela yokuhlaziya yokuhlonza kanye nokwenza iphrofayela yesidakamizwa inyaope etholakala emgwaqeni, kusetshenziswa isisi ichromatography-mass spectrometry. Lolu cwaningo lwathola okokuqala ngqa isincibilikisi esifaneleka kakhulu se-organic lapho izingxenye ezivamile zenyaope, okuyi-Δ9 -tetrahydrocannabinol, i-heroin, i-caffeine, i-dextromethorphan, i-phenacetin kanye nezidambisigciwane i-efavirenz kanye ne-nevirapine, ezinezici zamakhemikhali ezihlukene, zizinzile ngaphambi kokuhlaziywa kwamasampula enyaope. Izingxenye eziyinhloko zenyaope, lapho zikhishwa ku-tertiary butyl alcohol, zibonise ukuzinza okukhulu kwe-autosampler okungafika emahoreni angu-72 okugcina. Kule miphumela kunganqunywa ukuthi i-tertiary butyl alcohol iyisixazululi esifanelekile sokuhlonza, ukuqhathanisa nokuphrofayila amasampula e-nyaope. Mayelana nokuqinisekisa indlela yokuhlaziya, indlela inikeze ukuphindaphinda okwamukelekayo nge-%RSD ngaphansi kuka-10% kumazinga okugxilisa angu-10.0 no-1000.0 mg/L eningini lezingxenye. Ububanzi bokugxiliswa komugqa buphethwe umugqa ngo-r2 ≥ 0.997. Imikhawulo yokuthola ihluka phakathi kuka-9.90–39.0 pg kukholamu kanye nomkhawulo wenani phakathi kuka-30.0–120 pg kukholomu. Le ndlela ibonise ukululama okwamukelekayo nokumangelengele. Indlela ethuthukisiwe ifanele inhloso yobuningi bemininingwane yezingxenye ezinkulu zenyaope kusetshenziswa isisi ichromatography-mass spectrometry. Iningi lezingxenye zesidakamizwa sasemgwaqeni inyaope ziboniswe zizinzile okungenani amahora angu-24 uma zigcinwe esiqandisini. Ngezinjongo zokwenza iphrofayela, amasampuli adinga ukukhishwa phakathi namahora angu-24 okubanjwa ku-solvent lapho ezinzile khona, njenge-tertiary butyl alcohol futhi ahlaziywe phakathi namahora angu-72. Ngazo zonke izikhathi amasampula adinga ukuvikelwa ekukhanyeni ukuvimbela ukubola kwesithombe se-Δ9 -tetrahydrocannabinol kanye nomswakama ukuze kuvinjelwe i-hydrolysis ye-diamorphine. Izingxenye zamakhemikhali zamasampula enyaope alingisa kanye namasampula enyaope asemgwaqweni angempela ashaqwe ahlonzwe ngempumelelo futhi anqunywa ngokwenani kusetshenziswa isisi ichromatography - mass spectrometry. Amasampula ashaqwe emigwaqweni nalawo enziweyo ahlukaniswa ngempumelelo aba amaqoqo okuqala kusetshenziswa izingxenye zenyaope ezihlonziwe kanye nezindlela ezimbili ze-chemometric ezingagadiwe, okuwukuhlaziywa kwengxenye eyinhloko kanye nokuqoqwa kwezigaba, kanye namaphrofayili e-chromatographic. Ngakho-ke, ngokokuqala ngqá, indlela yokuhlaziya eqinisekisiwe iye yasungulwa ukuze kuhlonzwe, ukubala kanye nokwenza iphrofayela yenyaope kusetshenziswa isisi ichromatography-mass spectrometry. Indlela le izosiza ama-ejensi nomthetho ekuhlonzeni nasekuqhathaniseni amasampula enyaope futhi yenze kube lula ukushushiswa kwamacala okushushumbisa izidakamizwa. ___________________________________________________________________
Description
Thesis (Ph.D.(Genetics))--University of the Free State, 2020
Keywords
Heroin -- South Africa, Nyaope -- South Africa, Gas chromatography – mass spectrometry, Drugs -- Chemistry, Street cocktail
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