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Mechanistic formation of hazardous molecular heterocyclic amines from high temperature pyrolysis of model biomass materials: cellulose and tyrosine
BMC Chemistry ( IF 4.6 ) Pub Date : 2019-11-08 , DOI: 10.1186/s13065-019-0644-1
Samuel K Kirkok 1 , Joshua K Kibet 1 , Francis Okanga 1 , Thomas Kinyanjui 1 , Vincent Nyamori 2
Affiliation  

Research inventories on the co-pyrolysis of major biomass components such as cellulose with amino acid materials is scarce in literature despite the fact that such studies are critical in understanding toxic product relations from high temperature cooking, combustion of bio-fuels, cigarette smoking and forest fires. This paper explores, quantitatively, the yields of heterocyclic nitrogenated molecular reaction products of grave mutagenetic concern from the co-pyrolysis of model biomass materials; tyrosine and cellulose. Research has established that heterocyclic amines such as isocyanates are mutagens as well precursors for asthma, and other respiratory disorders. An equimassic mixture of tyrosine and cellulose (50 ± 2 mg) by weight were pyrolyzed in a tubular quartz reactor in flowing nitrogen at 1 atm. Besides, varying combinations of tyrosine and cellulose in the ratios 3:1 and 1:3 were also explored for comparison. The reaction time was set at 2 s so as to simulate combustions events in nature. The pyrolysate was collected over 5 mL dichloromethane and characterized using a gas chromatograph coupled to a mass spectrometer detector. Evidently, it was noted that 1-methylindazole was released in high yields at 300 °C, constituting ~ 300 µg in the entire pyrolysis temperature range (200–700 °C). Nonetheless, isoindazole gave the highest yield ~ 730 µg while 1-naphthyl isocyanate gave a total yield of ~ 336 µg in the same temperature range. Remarkably, the change in char yield between 300 and 450 °C for the pyrolysis of 25% tyrosine in 75% cellulose was found to be ~ 48% whereas the change in char yield for the pyrolysis of 75% tyrosine in 25% cellulose was 49%. The char and tar yields considered important residues of biomass burning have been reported in this study and found to be consistent with other research output in literature. The striking similarities of % yield of char across all temperatures for various combinations was the most significant observation in this investigation—char yield was independent of the mixing ratio during pyrolysis. From a mechanistic standpoint, it was noted that tyrosine inhibited cellulose based nitrogenated products. Thus N-products dominated the O-products.

中文翻译:

模型生物质材料高温热解形成有害分子杂环胺的机理:纤维素和酪氨酸

尽管这些研究对于了解高温烹饪、生物燃料燃烧、吸烟和森林产生的有毒产物关系至关重要,但文献中关于主要生物质成分(如纤维素)与氨基酸材料的共热解的研究清单很少火灾。本文定量探讨了模型生物质材料的共热解产生的具有严重诱变问题的杂环氮化分子反应产物的产率;酪氨酸和纤维素。研究已经确定,杂环胺如异氰酸酯是诱变剂,也是哮喘和其他呼吸系统疾病的前兆。在管状石英反应器中,在 1 atm 的流动氮气中热解酪氨酸和纤维素(50 ± 2 mg)重量的等质量混合物。除了,还探索了比例为 3:1 和 1:3 的酪氨酸和纤维素的不同组合以进行比较。反应时间设置为 2 秒,以模拟自然界中的燃烧事件。在 5 mL 二氯甲烷中收集热解物,并使用与质谱仪检测器耦合的气相色谱仪进行表征。显然,注意到 1-甲基吲唑在 300 °C 时以高产率释放,在整个热解温度范围 (200–700 °C) 中的释放量约为 300 µg。尽管如此,异吲唑的产量最高,约为 730 µg,而 1-萘基异氰酸酯在相同温度范围内的总产量约为 336 µg。值得注意的是,发现在 300 和 450 °C 之间热解 75% 纤维素中 25% 酪氨酸的炭产率变化约为 48%,而热解 25% 纤维素中 75% 酪氨酸的炭产率变化为 49%。本研究报告了被认为是生物质燃烧的重要残留物的焦炭和焦油产量,并发现与文献中的其他研究成果一致。各种组合在所有温度下的炭收率的惊人相似性是本研究中最重要的观察结果——炭收率与热解过程中的混合比无关。从机理的角度来看,注意到酪氨酸抑制了基于纤维素的氮化产物。因此,N 产品主导了 O 产品。本研究报告了被认为是生物质燃烧的重要残留物的焦炭和焦油产量,并发现与文献中的其他研究成果一致。各种组合在所有温度下的炭收率的惊人相似性是本研究中最重要的观察结果——炭收率与热解过程中的混合比无关。从机理的角度来看,注意到酪氨酸抑制了基于纤维素的氮化产物。因此,N 产品主导了 O 产品。本研究报告了被认为是生物质燃烧的重要残留物的焦炭和焦油产量,并发现与文献中的其他研究成果一致。各种组合在所有温度下的炭收率的惊人相似性是本研究中最重要的观察结果——炭收率与热解过程中的混合比无关。从机理的角度来看,注意到酪氨酸抑制了基于纤维素的氮化产物。因此,N 产品主导了 O 产品。从机理的角度来看,注意到酪氨酸抑制了基于纤维素的氮化产物。因此,N 产品主导了 O 产品。从机理的角度来看,注意到酪氨酸抑制了基于纤维素的氮化产物。因此,N 产品主导了 O 产品。
更新日期:2020-04-22
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