Alonso-Amelot Miguel E, Oliveros-Bastidas Alberto
Departamento de Química, Facultad de Ciencias, Grupo de Química Ecológica, Universidad de Los Andes, Mérida 5101, Venezuela.
J Chem Ecol. 2005 Feb;31(2):315-31. doi: 10.1007/s10886-005-1343-z.
The time-dependent natural release of hydrogen cyanide (HCN) was studied quantitatively using young croziers of the neotropical bracken fern Pteridium arachnoideum. HCN production was quantified in crushed tissue using a flow reactor at 30.0 +/- 0.1 degrees C. Released HCN was carried into appropriate traps with a moist air flow. Aliquots were drawn from the traps at fixed time intervals, and the HCN concentration was evaluated spectroscopically. All available prunasin (Pru), the only cyanogenic glycoside present, underwent decomposition into HCN in less than 1200 min. Fiddleheads (N = 76) contained 1.84-107.70 mg Pru g(1) dw in a continuous fashion suggesting genetic polymorphism. Acyanogenic morphs were rare (1/77). From the kinetics of the samples with Pru content near the median histographic distribution (N = 46), accumulated HCN formation as a function of time, initial velocities, average HCN production rate, and corresponding rate equations were obtained. Initial and average velocities correlated well with total Pru content. The yield of cyanide liberation varied widely between 0.51 and 47.86 microg HCN min(-1) g(-1) dw and was a linear function of [Pru]t. However, the beta-glucosidase enzyme involved in this reaction was not rate limiting and occurs in excess in the natural system. Enzyme activity was found to be independent of [Pru]t. The contribution of HCN as an allomone-upon-request against herbivores was assessed quantitatively. Bracken fiddleheads produced a pulse of HCN soon after tissue injury that waned rapidly, leaving a large portion of intact prunasin to decompose more slowly in the herbivore's lumen. The balance between the external and internal courses was found to depend on the concentration of prunasin in the plant, the amount of crozier eaten, and the time used to consume it.
利用新热带地区的蕨菜(Pteridium arachnoideum)幼叶拳卷体对氰化氢(HCN)随时间的自然释放进行了定量研究。在30.0±0.1℃下,使用流动反应器对粉碎组织中的HCN生成量进行定量。释放出的HCN通过潮湿空气流带入合适的捕集器中。在固定时间间隔从捕集器中抽取等分试样,并通过光谱法评估HCN浓度。所有可用的苦杏仁苷(Pru)是唯一存在的含氰糖苷,在不到1200分钟内分解为HCN。拳卷体(N = 76)以连续方式含有1.84 - 107.70 mg Pru g⁻¹干重,表明存在遗传多态性。非产氰形态很少见(1/77)。从苦杏仁苷含量接近直方图中位数分布的样品(N = 46)的动力学中,获得了累积HCN生成量随时间的变化、初始速度、平均HCN生成速率以及相应的速率方程。初始速度和平均速度与总苦杏仁苷含量相关性良好。氰化物释放量在0.51至47.86 μg HCN min⁻¹ g⁻¹干重之间变化很大,并且是[Pru]t的线性函数。然而,参与该反应的β - 葡萄糖苷酶不是限速因素,在自然系统中过量存在。发现酶活性与[Pru]t无关。定量评估了HCN作为一种按需产生的异种信息素对食草动物的作用。蕨菜拳卷体在组织受伤后很快产生一阵HCN,随后迅速减弱,留下大部分完整的苦杏仁苷在食草动物的消化道中更缓慢地分解。发现外部和内部过程之间的平衡取决于植物中苦杏仁苷的浓度、食用的拳卷体数量以及食用所用的时间。