著者

松本 謙吾 掛橋 秀直 鎌田 寛恵 志摩 典明 鎌田 徹 片木 宗弘 西岡 裕

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.28, no.2, pp.103-112, 2023 (Released:2023-07-31)

参考文献数

16

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Cannabidiol (CBD), an uncontrolled cannabinoid in marijuana, is readily converted to the controlled Δ9- and Δ8-THCs under acidic conditions. In this study, we monitored the time-course conversion of CBD into the two THCs using easily available acids and solvents by gas chromatography-mass spectrometry. Placing CBD (3.3 mg/mL) in 4.2 mM sulfuric acid-glacial acetic acid solution at room temperature resulted in the production of Δ9-Tetrahydrocannabinol (Δ9-THC) after 3 hours, followed by Δ8-THC after 96 hours. The conversion continued, and their relative abundance was Δ9-THC>CBD>Δ8-THC after 192 hours. Elevating the sulfuric acid concentration to 42 mM promoted the conversion to where CBD depleted in 3 hours, Δ9-THC production peaked (and started to decline) at 12 hours, and Δ8-THC became the major constituent at 100 hours. Replacing sulfuric acid with muriatic acid showed the similar time-course conversion. The THCs/CBD ratio varies under acidic conditions; this ratio can be used as an indicator for identifying the product lots of liquid drugs containing THCs converted from CBD. Ethanol, alternative solvent to glacial acetic acid, kept CBD unchanged with 42 mM sulfuric acid for 192 hours at room temperature, but conversion into Δ9-THC was observed after 6 hours when heated at 70℃. Without an acid catalyst, CBD was stable under heating cycles from 60℃ to 130℃ in an electric vaporizer. Thus, the unintentional production of THCs seems unlikely only by heating a commercial CBD product. The CBD-to-THCs conversion also yielded several by-products. Among them, possible Δ8-iso-THC was detected under all 12 combination conditions (two catalytic acids and six solvents) investigated in this study. Additionally, the use of alcohol solvents produced alcohol adducts of the THCs. Detection of by-products therefore can provide more solid information for identifying the product lots and estimating the condition of CBD conversion.

著者

浅井 龍太郎 鎌田 徹 新田 篤志 和田 美暁 掛橋 秀直 中野 史保子 松田 駿太朗 志摩 典明 西岡 裕 三木 昭宏 片木 宗弘

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.24, no.1, pp.43-48, 2019 (Released:2019-01-31)

参考文献数

18

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In order to expose substituted, cheated and faked urine specimens submitted for a drug test, a simple and highly sensitive screening method has been developed for the detection of urea in the specimens. This method uses the coloration of a piece of pH test paper which is wetted and set into the headspace of a sample vial containing “urine”, by absorbing NH3 gas generated by the urease reaction. The present method named, “Urease-Headspace method” (UHS method), was evaluated by applying it to various diluted or adulterated urine samples. The detection limit of urea in water was 2×10−4%, which was 100 times higher sensitivity compared with a conventional p-(dimethylamino)cinnamaldehyde (DAC) test. The UHS method was applicable even to deeply colored specimens such as bloody urine because the coloration occurs in the headspace of the sample vial. The UHS method quickly revealed the substituted specimens, e.g. water and green tea. Thus, the present UHS method will be effective for the validity determination of urine specimens, which is increasingly crucial in forensic drug examination.

著者

財津 桂 片木 宗弘 中西 啓子 志摩 典明 鎌田 寛恵 鎌田 徹 西岡 裕 三木 昭宏 辰野 道昭 岩村 樹憲 佐藤 貴子 土橋 均 鈴木 廣一

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.16, no.2, pp.73-90, 2011 (Released:2011-08-12)

参考文献数

31

被引用文献数

4 3

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Comprehensive analytical method to identify 11 kinds of synthetic cannabinoids has been investigated by thin layer chromatography (TLC), gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The analytes used in this study have already been detected from various herbal-type designer drugs: 8 kinds of aminoalkylindoles (AAIs) (JWH-015, JWH-018, JWH-073, JWH-081, JWH-200, JWH-250, JWH-251 and JWH-398), two kinds of cyclohexylphenols (CPs) (CP 47,497 and Cannabicyclohexanol), and a Δ9-tetrahydrocannabinol analog (HU-210).   Although specific color changes were observed for the cannabinoids using Marquis reagent, identification of each analyte based on Rf values was difficult to be obtained by TLC.   On the other hand, GC/MS and LC/MS/MS were appropriate for their qualitative analyses because of their chromatographic and mass spectral differentiation. A semi-polar capillary column DB-5MS showed the best separation and retention properties of the targeted cannabinoids among the tested GC column phases. Also, characteristic fragment ions were observed in each electron ionization-mass spectrum. The observed fragment ions were mainly derived from α-cleavage of ketone and α-cleavage of amine for AAIs, simple cleavage for CPs, and McLafferty rearrangements for HU-210.   Based on the ionization efficiency of the target analytes using LC/MS/MS, electrospray ionization positive mode was selected for AAIs, and negative mode for CPs and HU-210. All analytes were completely separated by gradient elution of ammonium formate aqueous solution-acetonitrile mobile phase on a C18 (ODS) separation column. In addition, characteristic fragment ions were observed in product ion spectra of AAIs and second generation product ion spectra of CPs and HU-210, enabling reliable confirmation.   These results provide useful information not only for simultaneous analyses of the targeted cannabinoids but also for structural assignment of future cannabimimetic compounds that may appear in the illicit drug market.

著者

西岡 裕 西川 眞弓 土橋 均

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.11, no.1, pp.53-75, 2006

被引用文献数

1

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A fully automated identification system for 35 benzodiazepines and their 29 metabolites was developed by gas chromatography-mass spectrometry (GC-MS) with a DB-5MS fused silica capillary column after trimethylsilyl (TMS) and trifluoroacetyl (TFA) derivatization, followed by registering both their retention times and mass spectra as the standard library data.<br>All the analytes except for rilmazafone and haloxazolam were detectable with and/or without TMS derivatization. TFA derivatization was found to be more effective in the more sensitive analysis of oxazolo-benzodiazepines except for flutazolam. Also, correction of their retention times by alkanes enabled to accurately identify on the different GC-MS systems with different lots of columns.<br>The present system allowed us to identify benzodiazepines and their metabolites in urine and blood more readily in a much shorter time, and it will be a powerful system for the analysis of benzodiazepines in the forensic chemistry and toxicology fields.

著者

松田 駿太朗 掛橋 秀直 中野 史保子 志摩 典明 鎌田 徹 西岡 裕 三木 昭宏 坂本 雄紀 宮川 治彦 草野 麻衣子 財津 桂 土橋 均 片木 宗弘

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.22, no.2, pp.109-121, 2017 (Released:2017-07-27)

参考文献数

13

被引用文献数

3

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In this study, we describe a rapid gas chromatography-tandem mass spectrometry (GC-MS/MS) analytical method that allows comprehensive detection and structural elucidation of synthetic cathinone-type designer drugs. Our proposed method consists of three simultaneous analytical procedures: 1) selective detection of the carbonyl group characteristic to each cathinone examined via selected reaction monitoring (SRM); and the determination of both 2) iminium cations and 3) substituted benzoyl cations generated via the α-cleavage of their corresponding amines and ketone moieties via product ion scanning, respectively.  One peak was detected in the SRM chromatogram for all cathinones examined in procedure 1), as well as the relevant single peaks in the total ion current chromatograms that resulted from procedures 2) and 3) at the same retention time. SRM of procedure 1) showed the transition of substituted benzoyl cations to substituted phenyl cations due to CO elimination, revealing the presence of carbonyl groups within the structures. Each product ion spectrum of the substituted benzoyl cation allowed for both determination of which group was substituted on the aromatic ring and differentiation between corresponding positional isomers for ethyl, methoxy and methylenedioxy substitution. However, identification of the substitution positions for the methyl, bromine and fluorine groups on the aromatic ring was difficult. On the other hand, differences between structural isomers in the product ion spectra of iminium cations were clearly identifiable, allowing for easy discrimination between isomers.

著者

掛橋 秀直 志摩 典明 鎌田 寛恵 松田 駿太朗 中野 史保子 和田 美暁 佐々木 啓子 鎌田 徹 西岡 裕 財津 桂 土橋 均 三木 昭宏 片木 宗弘

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.22, no.2, pp.77-90, 2017 (Released:2017-07-27)

参考文献数

26

被引用文献数

1

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Three analogues of 1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PVP), 1-(4-fluorophenyl)-2-(pyrolidin-1-yl)pentan-1-one (4F-α-PVP), 1-(4-methoxyphenyl)-2-(pyrrolidin-1-yl)pentan-1-one (4MeO-α-PVP) and 2-(pyrrolidin-1-yl)-1-(thiophen-2-yl)pentan-1-one (α-PVT), and their metabolites were determined in users' urine by liquid chromatography-tandem mass spectrometry using newly synthesized authentic standards. The identified metabolites indicated that metabolic pathways of three α-PVP analogues include the reduction of the carbonyl group to the corresponding alcohols and the oxidation of the pyrrolidine ring to the corresponding pyrrolidone, and 4MeO-α-PVP and α-PVT have additional metabolic pathways of the O-demethylation and the oxidation of thienyl group respectively. The quantitative analyses of the urinary metabolites suggested that the main metabolic pathways of these α-pyrrolidinophenones (PPs) derivatives could vary largely depending on the aromatic rings or substituent groups on the aromatic ring of PPs.

著者

掛橋 秀直 鎌田 寛恵 石川 亜香里 浅井 龍太郎 新田 篤志 和田 美暁 中野 史保子 松田 駿太朗 佐々木 啓子 志摩 典明 鎌田 徹 西岡 裕 三木 昭宏 片木 宗弘

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.24, no.1, pp.73-78, 2019 (Released:2019-01-31)

参考文献数

6

被引用文献数

2

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N-tert-Butoxycarbonyl-methamphetamine (t-BOCMA), a tert-butoxycarbonyl (t-BOC) derivative of methamphetamine (MA), which has recently been reported in several countries, was seized for the first time in Japan in 2017. It deprotected easily in an acidic condition to result in an illicit MA, and recently became a newly designated drug of the Pharmaceutical and Medical Device Act. For drug enforcement, the information of its properties was, therefore, strongly demanded. In this study, we synthesized the t-BOCMA standard, acquired various analytical data, and demonstrated its conversion to MA in high yield in the relatively moderate acidic condition (5% HCl methanol solution, 50℃). Also, the stability of t-BOCMA in simulated gastric juice (0.08 M HCl, 37℃) was explored by using GC/MS. As the result, 19% of t-BOCMA remained even after 120 min incubation, and the T1/2 was calculated to be 50 min. These suggest that the orally ingested t-BOCMA would be absorbed into blood in some degree without conversion to MA.

著者

松田 駿太朗 片木 宗弘 西岡 裕 鎌田 寛恵 佐々木 啓子 志摩 典明 鎌田 徹 三木 昭宏 辰野 道昭 財津 桂 坪井 健人 土橋 均 鈴木 廣一

出版者

日本法科学技術学会

雑誌

日本法科学技術学会誌 (ISSN:18801323)

巻号頁・発行日

vol.19, no.2, pp.77-89, 2014 (Released:2014-07-30)

参考文献数

12

被引用文献数

12 19

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Cathinone-type designer drugs are a newly-encountered drug family that has a β-ketophenethylamine skeleton. Recently, the abuse of these drugs has been increasingly common among young adults, and this has caused a serious social problem in many countries. Many of those drugs have become regulated by the Pharmaceutical Affairs Act, and some of them were later banned by the Narcotics and Psychotropics Control Act in Japan, depending on their structures. In this paper, a total of 98 standards of cathinone-type designer drugs were synthesized, and their EI-mass spectra were acquired by GC/MS, with and without trifluoroacetylation. For their free bases, a major fragment ion formed from the α-cleavage of the amine nitrogen was commonly observed. Also, a small fragment ion generated by the α-cleavage of the carbonyl group, followed by the elimination of CO was detectable. For the analogs having an N-alkyl chain longer than methyl group and/or the alkyl side-chain longer than methyl group, a characteristic ion formed from the α-cleavage of the amine nitrogen, followed by the elimination of the olefin moiety was observed. For the trifluoroacetyl derivatives, the intensity of fragment ion formed from the α-cleavage of carbonyl group significantly increased, while that of the fragment ion generated from the α-cleavage of nitrogen decreased, when compared with those of free bases. Also, the ion at m/z 110 was specifically observed for the cathinone analogs having a methylamino group. Those typical fragmentation patterns revealed by analyzing a series of analogs provide useful information for the characterization of cathinone-type designer drugs.