Dudek Monika, Machalska Ewa, Oleszkiewicz Tomasz, Grzebelus Ewa, Baranski Rafal, Szcześniak Piotr, Mlynarski Jacek, Zajac Grzegorz, Kaczor Agnieszka, Baranska Malgorzata
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387, Cracow, Poland.
Institute of Plant Biology and Biotechnology, Faculty of Biotechnology and Horticulture, University of Agriculture in Krakow, AL. 29 Listopada 54, 31-425, Cracow, Poland.
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8383-8388. doi: 10.1002/anie.201901441. Epub 2019 May 14.
Carotenoid microcrystals, extracted from cells of carrot roots and consisting of 95 % of achiral β-carotene, exhibit a very intense chiroptical (ECD and ROA) signal. The preferential chirality of crystalline aggregates that consist mostly of achiral building blocks is a newly observed phenomenon in nature, and may be related to asymmetric information transfer from the chiral seeds (small amount of α-carotene or lutein) present in carrot cells. To confirm this hypothesis, we synthesized several model aggregates from various achiral and chiral carotenoids. Because of the sergeant-and-soldier behavior, a small number of chiral sergeants (α-carotene or astaxanthin) force the achiral soldier molecules (β- or 11,11'-[D ]-β-carotene) to jointly form supramolecular assemblies of induced chirality. The chiral amplification observed in these model systems confirmed that chiral microcrystals appearing in nature might consist predominantly of achiral building blocks and their supramolecular chirality might result from the co-crystallization of chiral and achiral analogues.
从胡萝卜根细胞中提取的类胡萝卜素微晶，由95%的非手性β-胡萝卜素组成，表现出非常强烈的手性光学（ECD和ROA）信号。主要由非手性结构单元组成的晶体聚集体的优先手性是自然界中一种新观察到的现象，可能与胡萝卜细胞中存在的手性种子（少量α-胡萝卜素或叶黄素）的不对称信息传递有关。为了证实这一假设，我们从各种非手性和手性类胡萝卜素合成了几种模型聚集体。由于“士兵-中士”行为，少量手性中士（α-胡萝卜素或虾青素）迫使非手性士兵分子（β-或11,11'-[D]-β-胡萝卜素）共同形成诱导手性的超分子组装体。在这些模型系统中观察到的手性放大证实，自然界中出现的手性微晶可能主要由非手性结构单元组成，其超分子手性可能是手性和非手性类似物共结晶的结果。
