Crop and Soil Science Department, Oregon State University, 3050 SW Campus Way, Corvallis, OR, 97331, USA.
School of Pharmacy, University of Camerino, via Sant' Agostino 1, 62032, Camerino, Italy.
Sci Rep. 2021 Oct 6;11(1):19890. doi: 10.1038/s41598-021-99335-4.
Hemp (Cannabis sativa L.) synthesizes and accumulates a number of secondary metabolites such as terpenes and cannabinoids. They are mostly deposited as resin into the glandular trichomes occurring on the leaves and, to a major extent, on the flower bracts. In the last few years, hemp for production of high-value chemicals became a major commodity in the U.S. and across the world. The hypothesis was that hemp biomass valorization can be achieved through distillation and procurement of two high-value products: the essential oil (EO) and cannabinoids. Furthermore, the secondary hypothesis was that the distillation process will decarboxylate cannabinoids hence improving cannabinoid composition of extracted hemp biomass. Therefore, this study elucidated the effect of steam distillation on changes in the content and compositional profile of cannabinoids in the extracted biomass. Certified organic CBD-hemp strains (chemovars, varieties) Red Bordeaux, Cherry Wine and Umpqua (flowers and some upper leaves) and a T&H strain that included chopped whole-plant biomass, were subjected to steam distillation, and the EO and cannabinoids profile were analyzed by gas chromatography-mass spectrometry (GC-MS) and HPLC, respectively. The distillation of hemp resulted in apparent decarboxylation and conversion of cannabinoids in the distilled biomass. The study demonstrated a simple method for valorization of CBD-hemp through the production of two high-value chemicals, i.e. EO and cannabinoids with improved profile through the conversion of cannabidiolic acid (CBD-A) into cannabidiol (CBD), cannabichromenic acid (CBC-A) into cannabichromene (CBC), cannabidivarinic acid (CBDV-A) into cannabidivarin (CBDV), cannabigerolic acid (CBG-A) into cannabigerol (CBG), and δ-9-tetrahydrocannabinolic acid (THC-A) into δ-9-tetrahydrocannabinol (THC). In addition, the distilled biomass contained CBN while the non-distilled did not. Distillation improved the cannabinoids profile; e.g. the distilled hemp biomass had 3.4 times higher CBD in variety Red Bordeaux, 5.6 times in Cherry Wine, 9 times in variety Umpqua, and 6 times in T&H compared to the original non-distilled samples, respectively. Most of the cannabinoids remained in the distilled biomass and small amounts of CBD were transferred to the EO. The CBD concentration in the EO was as follows: 5.3% in the EO of Umpqua, 0.15% in the EO of Cherry Wine and Red Bordeaux and 0.06% in the EO of T&H. The main 3 EO constituents were similar but in different ratio; myrcene (23.2%), (E)-caryophyllene (16.7%) and selina-3,7(11)-diene (9.6%) in Cherry Wine; (E)-caryophyllene (~ 20%), myrcene (16.6%), selina-3,7(11)-diene (9.6%), α-humulene (8.0%) in Red Bordeaux; (E)-caryophyllene (18.2%) guaiol (7.0%), 10-epi-γ-eudesmol (6.9%) in Umpqua; and (E)-caryophyllene (30.5%), α-humulene (9.1%), and (E)-α-bisabolene (6.5%) in T&H. In addition, distillation reduced total THC in the distilled biomass. Scanning electron microscopy (SEM) analyses revealed that most of the glandular trichomes in the distilled biomass were not disturbed (remained intact); that suggest a possibility for terpenes evaporation through the epidermal membrane covering the glandular trichomes leaving the cannabinoids in the trichomes. This explained the fact that distillation resulted in terpene extraction while the cannabinoids remained in the distilled material.
大麻(Cannabis sativa L.)合成并积累了许多次生代谢产物,如萜烯和大麻素。它们主要以树脂的形式沉积在叶上,尤其是在花苞片上的腺毛中。在过去的几年中,用于生产高价值化学品的大麻已成为美国和全球的主要商品。假设是通过蒸馏和采购两种高价值产品:精油(EO)和大麻素,可以实现大麻生物质的增值。此外,还有一个次要假设是,蒸馏过程会使大麻素脱羧,从而改善提取大麻生物质中的大麻素组成。因此,本研究阐明了蒸汽蒸馏对提取生物质中大麻素含量和组成特征变化的影响。经过认证的有机 CBD-大麻品种(化学型、品种)红波尔多、樱桃酒和昂普夸(花和一些上部叶片)和包括切碎的全植物生物质的 T&H 品种,经过蒸汽蒸馏,通过气相色谱-质谱联用(GC-MS)和高效液相色谱(HPLC)分别分析精油和大麻素的特征。大麻的蒸馏导致蒸馏生物质中明显的脱羧和大麻素转化。该研究证明了通过生产两种高价值化学品(即精油和大麻素)来增值 CBD-大麻的简单方法,通过将大麻二酚酸(CBD-A)转化为大麻二酚(CBD)、大麻色烯酸(CBC-A)转化为大麻色烯(CBC)、大麻二酚酸(CBDV-A)转化为大麻二酚(CBDV)、大麻二醇酸(CBG-A)转化为大麻二醇(CBG)和 δ-9-四氢大麻酚酸(THC-A)转化为 δ-9-四氢大麻酚(THC)来改善大麻素的特征。此外,蒸馏后的生物质中含有 CBN,而未蒸馏的则没有。蒸馏改善了大麻素特征;例如,与原始未蒸馏的样品相比,品种红波尔多的 CBD 含量提高了 3.4 倍,樱桃酒提高了 5.6 倍,品种昂普夸提高了 9 倍,T&H 提高了 6 倍。大多数大麻素仍保留在蒸馏后的生物质中,少量 CBD 转移到精油中。精油中的 CBD 浓度如下:昂普夸精油中的 CBD 浓度为 5.3%,樱桃酒精油中的 CBD 浓度为 0.15%,红波尔多精油中的 CBD 浓度为 0.06%,T&H 精油中的 CBD 浓度为 0.06%。主要的 3 种精油成分相似,但比例不同;樱桃酒中的主要成分是(E)-石竹烯(23.2%)、(E)-丁香烯(16.7%)和蛇麻烯-3,7(11)-二烯(9.6%);红波尔多中的主要成分是(E)-丁香烯(~20%)、(E)-石竹烯(16.6%)、蛇麻烯-3,7(11)-二烯(9.6%)、α-葎草烯(8.0%);昂普夸中的主要成分是(E)-丁香烯(18.2%)、愈创木酚(7.0%)、10-表-γ-桉叶油醇(6.9%);T&H 中的主要成分是(E)-丁香烯(30.5%)、α-葎草烯(9.1%)和(E)-α-毕澄茄烯(6.5%)。此外,蒸馏降低了蒸馏生物质中的总 THC。扫描电子显微镜(SEM)分析表明,蒸馏后的生物质中的大多数腺毛没有受到干扰(保持完整);这表明萜烯可能通过覆盖腺毛的表皮膜蒸发,而大麻素则留在腺毛中。这解释了蒸馏导致萜烯提取而大麻素仍留在蒸馏材料中的事实。