冰片

冰片
冰片
	IUPAC名; endo-1,7,7-Trimethyl- bicyclo[2.2.1]heptan-2-ol
識別
CAS號	507-70-0 ; 464-43-7（(+)） ; 464-45-9（(-)）
PubChem	6552009
ChemSpider	5026296
SMILES	CC1(C2(C)C)C(O)CC2CC1;
InChI	1/C10H18O/c1-9(2)7-4-5-10(9,3)8(11)6-7/h7-8,11H,4-6H2,1-3H3/t7-,8+,10+/m1/s1;
InChIKey	DTGKSKDOIYIVQL-WEDXCCLWBQ
ChEBI	15393
KEGG	C01411
IUPHAR配體	6413
性質
化學式	C10H18O
密度	1.011 g/cm3 @ 20oC
熔點	208°C
沸點	易升華
危險性
	歐盟危險性符號; 有害 Xn 易燃 F
警示術語	R：R33-R36/37/38
安全術語	S：S26-S37
MSDS	英文MSDS
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

冰片（分子式：C₁₀H₁₈O），又名片腦、桔片、龍腦香、梅花冰片、羯布羅香、梅花腦、冰片腦、梅冰、龍腦、瑞腦、腦子、天然冰片、老梅片、梅片等，是由2個異戊二烯結構單元組成的環狀化合物，屬於單萜衍生物^[1]。根據旋光性分為左旋龍腦和右旋龍腦^[2]。右旋龍腦主要來源於龍腦樟和陰香樹^[3]，而左旋龍腦主要來源於菊科植物^[4]。

合成

生物合成

冰片的合成前體由細胞質中的甲羥戊酸途徑和質體中的4-磷酸-2-甲基赤蘚糖途徑產生的異戊烯基焦磷酸和二甲基烯丙基焦磷酸合成^[5]。在香葉基焦磷酸合酶的催化作用下，這些合成物縮合生成香葉基焦磷酸^[6]，隨後在二磷酸龍腦合酶的作用下環化成二磷酸龍腦，最終在鹼性磷酸酶的作用下脫去磷酸基團生成龍腦^[2]。

冰片的手性具體取決於二磷酸龍腦合酶偏好的手性。目前已知一個二磷酸左旋龍腦合成酶的序列和多個二磷酸右旋龍腦合成酶的序列。^[7]

此外，龍腦在龍腦脫氫酶的催化作用下被氧化成樟腦^[8]。

人工合成

冰片極易被氧化成酮而生成樟腦，人工合成方法是通過Meerwein–Ponndorf–Verley還原反應將樟腦還原成冰片。中國所謂「合成冰片」是以消旋樟腦為起點，得到的冰片和異冰片的消旋混合物。「半合成冰片」則是以單獨一個手性樟腦開始：(+)-樟腦還原可得(+)-冰片和(-)-異冰片。^[9]

加入硼氫化鈉可以加快反應速率，使反應成為不可逆反應，但是產物也由於動力學控制變成異冰片。

樟腦被還原成異冰片

利用

冰片被認為具有抗菌、保護心腦血管、鎮痛消炎、防止血栓、促進藥物透過血腦屏障等多種作用^[10]。常應用於臨床治療，作為止痛劑、鎮痛劑和麻醉劑^[11]。

毒性

冰片具有劑量毒性，大量使用會引起毒性反應。^[12]

參考資料

^ Wang, Hong; Ma, Dongming; Yang, Jinfen; Deng, Ke; Li, Meng; Ji, Xiaoyu; Zhong, Liting; Zhao, Haiying. An Integrative Volatile Terpenoid Profiling and Transcriptomics Analysis for Gene Mining and Functional Characterization of AvBPPS and AvPS Involved in the Monoterpenoid Biosynthesis in Amomum villosum. Frontiers in Plant Science. 2018-06-20, 9. doi:10.3389/fpls.2018.00846.
^ ^2.0 ^2.1 Chen, Changjie; Miao, Yuhuan; Luo, Dandan; Wang, Zixin; Guo, Lujuan; Zhao, Tingting; Liu, Dahui. Cloning and Functional Verification of the Borneol Dehydrogenase Encoding Gene AArBDH1 in Artemisia argyi. Chinese Bulletin of Botany. 2023-07-01, 58 (4): 560. doi:10.11983/CBB22123.
^ Xingxing, Liu; Xi, Zhang; Xiali, Guo; Shangji, Gong; Xiangmei, Jiang; Yuxin, Fu; Liping, Luo. Multivariate Analyses of Volatile Chemical Composition in Leaves of Different Cinnamomum camphora Chemotypes. Chinese Bulletin of Botany. 2014, 49 (2): 161. doi:10.3724/SP.J.1259.2014.00161.
^ Ho, Tsung-Jung; Hung, Chien-Che; Shih, Tzenge-Lien; Yiin, Lih-Ming; Chen, Hao-Ping. Investigation of borneols sold in Taiwan by chiral gas chromatography. Journal of Food and Drug Analysis. 2018-01, 26 (1): 348–352. doi:10.1016/j.jfda.2016.10.012.
^ 徐應文; 呂季娟; 吳衛; 鄭有良. 植物单萜合酶研究进展. 生態學報. 2009, 29 (6): 3188–3197 [2024-03-10]. ISSN 1000-0933. CNKI STXB200906052. （原始內容存檔於2024-03-10）.
^ 趙圓圓; 孫葉雯; 鄭詩敏; 李萌; 馬東明; 楊錦芬. 阳春砂龙脑基二磷酸合酶关键氨基酸位点筛选及突变体的构建. 中草藥. 2022, 53 (2): 529–537 [2024-03-10]. doi:10.7501/j.issn.0253-2670.2022.02.023. CNKI ZCYO202202022. （原始內容存檔於2024-03-10）.
^ Ma, Rui; Su, Ping; Ma, Qing; Guo, Juan; Chen, Suiqing; Jin, Baolong; Zhang, Haiyan; Tang, Jinfu; Zhou, Tao; Xiao, Chenghong; Cui, Guanghong; Huang, Luqi. Identification of (-)-bornyl diphosphate synthase from Blumea balsamifera and its application for (-)-borneol biosynthesis in Saccharomyces cerevisiae. Synthetic and Systems Biotechnology. 2022-03, 7 (1): 490–497. PMC 8671873  . PMID 34977393. doi:10.1016/j.synbio.2021.12.004.
^ Hurd, Matthew C.; Kwon, Moonhyuk; Ro, Dae-Kyun. Functional identification of a Lippia dulcis bornyl diphosphate synthase that contains a duplicated, inhibitory arginine-rich motif. Biochemical and Biophysical Research Communications. 2017-08, 490 (3): 963–968. doi:10.1016/j.bbrc.2017.06.147.
^ Yang, Ming‐Yeh; Khine, Aye Aye; Liu, Jen‐Wei; Cheng, Hui‐Chen; Hu, Anren; Chen, Hao‐Ping; Shih, Tzenge‐Lien. Resolution of isoborneol and its isomers by GC/MS to identify “synthetic” and “semi‐synthetic” borneol products. Chirality. November 2018, 30 (11): 1233–1239. doi:10.1002/chir.23017.
^ Ma, Rui; Su, Ping; Guo, Juan; Jin, Baolong; Ma, Qing; Zhang, Haiyan; Chen, Lingli; Mao, Liuying; Tian, Mei; Lai, Changjiangsheng; Tang, Jinfu; Cui, Guanghong; Huang, Luqi. Bornyl Diphosphate Synthase From Cinnamomum burmanni and Its Application for (+)-Borneol Biosynthesis in Yeast. Frontiers in Bioengineering and Biotechnology. 2021-02-11, 9. doi:10.3389/fbioe.2021.631863.
^ Khine, Aye Aye; Lu, Pei-Chieh; Ko, Tzu-Ping; Huang, Kai-Fa; Chen, Hao-Ping. Cloning, expression, identification and characterization of borneol dehydrogenase isozymes in Pseudomonas sp. TCU-HL1. Protein Expression and Purification. 2020-11, 175: 105715. doi:10.1016/j.pep.2020.105715.
^ Material Safety Data Sheet, Fisher Scientific. [2022-10-01]. （原始內容存檔於2022-10-04）.

外部連結

冰片中藥材圖像數據庫 (香港浸會大學中醫藥學院) （中文）（英文）
冰片 Bing Pian（頁面存檔備份，存於互聯網檔案館）中藥標本數據庫（香港浸會大學中醫藥學院）（繁體中文）（英文）
梅花冰片 Mei Hua Bing Pian（頁面存檔備份，存於互聯網檔案館）中藥標本數據庫（香港浸會大學中醫藥學院）（繁體中文）（英文）

[1] Wang, Hong; Ma, Dongming; Yang, Jinfen; Deng, Ke; Li, Meng; Ji, Xiaoyu; Zhong, Liting; Zhao, Haiying. An Integrative Volatile Terpenoid Profiling and Transcriptomics Analysis for Gene Mining and Functional Characterization of AvBPPS and AvPS Involved in the Monoterpenoid Biosynthesis in Amomum villosum. Frontiers in Plant Science. 2018-06-20, 9. doi:10.3389/fpls.2018.00846.

[CBB22123-2] 2.0 ^2.1 Chen, Changjie; Miao, Yuhuan; Luo, Dandan; Wang, Zixin; Guo, Lujuan; Zhao, Tingting; Liu, Dahui. Cloning and Functional Verification of the Borneol Dehydrogenase Encoding Gene AArBDH1 in Artemisia argyi. Chinese Bulletin of Botany. 2023-07-01, 58 (4): 560. doi:10.11983/CBB22123.

[3] Xingxing, Liu; Xi, Zhang; Xiali, Guo; Shangji, Gong; Xiangmei, Jiang; Yuxin, Fu; Liping, Luo. Multivariate Analyses of Volatile Chemical Composition in Leaves of Different Cinnamomum camphora Chemotypes. Chinese Bulletin of Botany. 2014, 49 (2): 161. doi:10.3724/SP.J.1259.2014.00161.

[4] Ho, Tsung-Jung; Hung, Chien-Che; Shih, Tzenge-Lien; Yiin, Lih-Ming; Chen, Hao-Ping. Investigation of borneols sold in Taiwan by chiral gas chromatography. Journal of Food and Drug Analysis. 2018-01, 26 (1): 348–352. doi:10.1016/j.jfda.2016.10.012.

[5] 徐應文; 呂季娟; 吳衛; 鄭有良. 植物单萜合酶研究进展. 生態學報. 2009, 29 (6): 3188–3197 [2024-03-10]. ISSN 1000-0933. CNKI STXB200906052. （原始內容存檔於2024-03-10）.

[6] 趙圓圓; 孫葉雯; 鄭詩敏; 李萌; 馬東明; 楊錦芬. 阳春砂龙脑基二磷酸合酶关键氨基酸位点筛选及突变体的构建. 中草藥. 2022, 53 (2): 529–537 [2024-03-10]. doi:10.7501/j.issn.0253-2670.2022.02.023. CNKI ZCYO202202022. （原始內容存檔於2024-03-10）.

[7] Ma, Rui; Su, Ping; Ma, Qing; Guo, Juan; Chen, Suiqing; Jin, Baolong; Zhang, Haiyan; Tang, Jinfu; Zhou, Tao; Xiao, Chenghong; Cui, Guanghong; Huang, Luqi. Identification of (-)-bornyl diphosphate synthase from Blumea balsamifera and its application for (-)-borneol biosynthesis in Saccharomyces cerevisiae. Synthetic and Systems Biotechnology. 2022-03, 7 (1): 490–497. PMC 8671873  . PMID 34977393. doi:10.1016/j.synbio.2021.12.004.

[8] Hurd, Matthew C.; Kwon, Moonhyuk; Ro, Dae-Kyun. Functional identification of a Lippia dulcis bornyl diphosphate synthase that contains a duplicated, inhibitory arginine-rich motif. Biochemical and Biophysical Research Communications. 2017-08, 490 (3): 963–968. doi:10.1016/j.bbrc.2017.06.147.

[9] Yang, Ming‐Yeh; Khine, Aye Aye; Liu, Jen‐Wei; Cheng, Hui‐Chen; Hu, Anren; Chen, Hao‐Ping; Shih, Tzenge‐Lien. Resolution of isoborneol and its isomers by GC/MS to identify “synthetic” and “semi‐synthetic” borneol products. Chirality. November 2018, 30 (11): 1233–1239. doi:10.1002/chir.23017.

[10] Ma, Rui; Su, Ping; Guo, Juan; Jin, Baolong; Ma, Qing; Zhang, Haiyan; Chen, Lingli; Mao, Liuying; Tian, Mei; Lai, Changjiangsheng; Tang, Jinfu; Cui, Guanghong; Huang, Luqi. Bornyl Diphosphate Synthase From Cinnamomum burmanni and Its Application for (+)-Borneol Biosynthesis in Yeast. Frontiers in Bioengineering and Biotechnology. 2021-02-11, 9. doi:10.3389/fbioe.2021.631863.

[11] Khine, Aye Aye; Lu, Pei-Chieh; Ko, Tzu-Ping; Huang, Kai-Fa; Chen, Hao-Ping. Cloning, expression, identification and characterization of borneol dehydrogenase isozymes in Pseudomonas sp. TCU-HL1. Protein Expression and Purification. 2020-11, 175: 105715. doi:10.1016/j.pep.2020.105715.

[12] Material Safety Data Sheet, Fisher Scientific. [2022-10-01]. （原始內容存檔於2022-10-04）.

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